Diketopyrrolopyrrole polymers as organic semiconductors

ABSTRACT

The present invention relates to polymers comprising a repeating unit of the formula (I) and their use as organic semiconductor in organic devices, especially a diode, an organic field effect transistor and/or a solar cell, or a device containing a diode and/or an organic field effect transistor, and/or a solar cell. The polymers according to the invention have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers according to the invention are used in semiconductor devices or organic photovoltaic (PV) devices (solar cells).

The present invention relates to polymers comprising a repeating unit ofthe formula (I) and their use as organic semiconductor in organicdevices, especially a diode, an organic field effect transistor and/or asolar cell, or a device containing a diode and/or an organic fieldeffect transistor, and/or a solar cell. The polymers according to theinvention have excellent solubility in organic solvents and excellentfilm-forming properties. In addition, high efficiency of energyconversion, excellent field-effect mobility, good on/off current ratiosand/or excellent stability can be observed, when the polymers accordingto the invention are used in semiconductor devices or organicphotovoltaic (PV) devices (solar cells).

M. Smet et al., Tetrahedron Lett. 42 (2001) 6527-6530 describe thepreparation of rod-like diketopyrrolopyrrole oligomers by a stepwisesequence of Suzuki couplings using brominated1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP) derivatives and1,4-dibromo-2,5-di-n-hexylbenzene as the monomers.

M. Horn et. al, Eur. Polymer J. 38 (2002) 2197-2205 describe thesynthesis and characterisation of thermomesogenic polysiloxanes with2,5-dihydropyrrolo[3,4-c]pyrrole units in the main chain.

EP-A-787,730 describes a polyacrylate and a polyurethane obtained by thepolymerization of a DPP of formula Ia

wherein Q₁ and Q₄ independently of each other stand for a polymerizablereactive group, and Q₂ and Q₃ independently of each other stand forhydrogen, C₁₂-C₂₄alkyl, C₆-C₂₄alkyl which is interrupted one or moretimes by O or S, or are a group of the formula

in which Q₅ is C₄-C₁₈alkyl or C₅-C₁₀cycloalkyl.

Though it is mentioned that compounds Ia can be used for the preparationof photo- and electroconductive polymers, no corresponding examples aregiven. Further, no teaching is given of how to prepare EL devicescomprising DPP-based polymers and of how to select the appropriateDPP-monomers resp. DPP-polymers.

Macromol. Chem. Phys. 200 (1999) 106-112 describes fluorescentDPP-polymers obtainable by the copolymerization of bifunctionalmonomeric DPP-derivatives, wherein the functional groups are attached tothe N-atoms of the DPP-molecule, with diisocyanates or di-ols ordi-acids.

J. Am. Chem. Soc. 117 (1995) 12426-12435 relates to the exploration ofthe palladium catalysed Stille coupling reaction for the synthesis offunctional polymers. In Scheme 7 the synthesis of the following polymersis presented:

No teaching is given whether the described polymers can be used in ELdevices.

J. Am. Chem. Soc. 115 (1993) 11735-11743 describes DPP-polymersdemonstrating photorefractivity, i.e. exhibiting photoconductivity andsecond order non-linear-optical activity. In this device,photoconductive properties are determined by irradiating the device witha laser beam and then measuring the current resulting from thisirradiation, no measurements were carried out with regard toelectroluminescence.

Further, no teaching is given of how to select other DPP-polymers.

In Appl. Phys. Lett. 64 (1994) 2489-2491 further studies, i.e. two-beamcoupling experiments, using polymers disclosed in J. Am. Chem. Soc. 115(1993) 11735-11743 are performed to study photorefractivity. Thetwo-beam coupling experiments demonstrated asymmetric energy exchangeunder zero field, i.e. photorefractivity of the polymers disclosed in J.Am. Chem. Soc. 115 (1993) 11735-11743.

U.S. Pat. No. 6,451,459 (cf. B. Tieke et al., Synth. Met. 130 (2002)115-119; Macromol. Rapid Commun. 21 (4) (2000) 182-189) describesdiketopyrrolopyrrole based polymers and copolymers comprising thefollowing units

wherein x is chosen in the range of from 0.005 to 1, preferably from0.01 to 1, and y from 0.995 to 0, preferably 0.99 to 0, and whereinx+y=1, andwherein Ar¹ and Ar² independently from each other stand for

and m, n being numbers from 1 to 10, andR¹ and R² independently from each other stand for H, C₁-C₁₈alkyl,—C(O)O—C₁-C₁₈alkyl, perfluoro-C₁-C₁2 alkyl, unsubstituted C₆-C₁₂aryl orone to three times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, or halogensubstituted C₆-C₁₂aryl, C₁-C₁₂alkyl-C₆-C₁₂aryl, orC₆-C₁₂aryl-C₁-C₁₂alkyl,R³ and R⁴ preferably stand for hydrogen, C₁-C₁₂alkyl, C₁-C₁₂alkoxy,unsubstituted C₆-C₁₂aryl or one to three times with C₁-C₁₂alkyl,C₁-C₁₂alkoxy, or halogen substituted C₆-C₁₂aryl orperfluoro-C₁-C₁₂alkyl, andR⁵ preferably stands for C₁-C₁₂alkyl, C₁-C₁₂alkoxy, unsubstitutedC₆-C₁₂aryl or one to three times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, orhalogen substituted C₆-C₁₂aryl, or perfluoro-C₁-C₁₂alkyl, and their usein EL devices. The following polymer

is explicitly disclosed in Tieke et al., Synth. Met. 130 (2002) 115-119.The following polymers

are explicitly disclosed in Macromol. Rapid Commun. 21 (4) (2000)182-189.

WO05/049695 discloses diketopyrrolopyrrole (DPP) based polymers andtheir use in PLEDs, organic integrated circuits (O-ICs), organic fieldeffect transistors (OFETs), organic thin film transistors (OTFTs),organic solar cells (O-SCs), or organic laser diodes, but fails todisclose the specific DPP based polymers of formula I. In Example 12 thepreparation of the following polymer is described:

The object of the present invention is to provide novel polymers whichshow excellent performance when used, for example, in semiconductordevices, photodiodes or organic photovoltaic (PV) devices (solar cells),such as high efficiency of energy conversion, excellent field-effectmobility, good on/off current ratios and/or excellent stability.

Said object is achieved by polymers comprising repeating units of theformula

wherein a, b, c, d, e and f are 0 to 200, especially 0, 1, 2, or 3;Ar¹ and Ar^(1′) are independently of each other a group of formula

Ar², Ar^(2′), Ar³, Ar^(3′), Ar⁴ and Ar^(4′) are independently of eachother a group of formula

p stands for 0, 1, 2, 3 or 4, if possible,R¹ and R² may be the same or different and are selected from hydrogen, aC₁-C₂₅alkyl group, an alkenyl group, an alkynyl group, which mayoptionally be substituted by E and/or interrupted by D, an allyl group,which can be substituted one to three times with C₁-C₄alkyl; acycloalkyl group, which can be substituted one to three times withC₁-C₈alkyl, C₁-C₈thioalkoxy, or C₁-C₈alkoxy, or a cycloalkyl group,which can be condensed one or two times by phenyl, which can besubstituted one to three times with C₁-C₄-alkyl, halogen, nitro orcyano; a cycloalkenyl group, a ketone or aldehyde group, an ester group,a carbamoyl group, a silyl group, a siloxanyl group, Ar¹⁰ or—CR⁵R⁶—(CH₂)_(g)Ar¹⁰, whereinR⁵ and R⁶ independently from each other stand for hydrogen, fluorine,cyano or C₁-C₄alkyl, which can be substituted by fluorine, chlorine orbromine, or phenyl, which can be substituted one to three times withC₁-C₄alkyl,Ar¹⁰ stands for aryl or heteroaryl, which may optionally be substitutedby G, in particular phenyl or 1- or 2-naphthyl which can be substitutedone to three times with C₁-C₈alkyl, C₁-C₈thioalkoxy, and/or C₁-C₈alkoxy,and g stands for 0, 1, 2, 3 or 4,R³ may be the same or different within one group and is selected fromC₁-C₂₅alkyl, which may optionally be substituted by E and/or interruptedby D, C₆-C₂₄aryl, which may optionally be substituted by G,C₂-C₂₀heteroaryl, which may optionally be substituted by G,C₁-C₁₈alkoxy, which may optionally be substituted by E and/orinterrupted by D, C₇-C₂₅aralkyl, wherein ar (=aryl) of aralkyl mayoptionally be substituted by G, or —CO—R²⁸, or two or more groups R³which are in the neighbourhood to each other, form a ring;R⁴, R^(4′), R⁷ and R^(7′) independently from each other stand forhydrogen, C₁-C₂₅alkyl, which may optionally be substituted by E and/orinterrupted by D, C₆-C₂₄aryl, which may optionally be substituted by G,C₂-C₂₀heteroaryl, which may optionally be substituted by G,C₁-C₁₈alkoxy, which may optionally be substituted by E and/orinterrupted by D, C₇-C₂₅aralkyl, wherein ar (=aryl) of aralkyl mayoptionally be substituted by G, or —CO—R²⁸; or R⁴ and R^(4′) form aring;

D is —CO—; —COO—; —S—; —SO—; —SO₂—; —NR²⁵—; —CR²³═CR²⁴—; or —C≡C—; and

E is —OR²⁹; —SR²⁹; —NR²⁵R²⁶; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁶; —CN; orhalogen; G is E, C₁-C₁₈alkyl, which may be interrupted by D, orC₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, whereinR²³, R²⁴, R²⁵ and R²⁶ are independently of each other H; C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—;R²⁷ and R²⁸ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—,R²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl,or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by—O—,R¹⁰⁹ and R¹¹⁰ are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, or C₇-C₂₅aralkyl, orR¹⁰⁹ and R¹¹⁰ together form a group of formula ═CR¹⁰⁰R¹⁰¹, whereinR¹⁰⁰ and R¹⁰¹ are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂-C₂₀heteroaryl,or C₂-C₂₀heteroaryl which is substituted by G, orR¹⁰⁹ and R¹¹⁰ together form a five or six membered ring, whichoptionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl whichis substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D,C₇-C₂₅aralkyl, or C(═O)—R¹⁸,R¹¹¹ is H, a C₁-C₂₅alkyl group, a C₄-C₁₈cycloalkyl group, a C₁-C₂₅alkoxygroup, in which one or more carbon atoms which are not in neighbourhoodto each other could be replaced by —O—, —S—, or —C(═O)—O—, and/orwherein one or more hydrogen atoms can be replaced by F, a C₆-C₂₄arylgroup, or a C₆-C₂₄aryloxy group, wherein one or more carbon atoms can bereplaced by O, S, or N, and/or which can be substituted by one or morenon-aromatic groups R¹¹¹;m can be the same or different at each occurrence and is 0, 1, 2, or 3,especially 0, 1, or 2, very especially 0 or 1;X¹ is a hydrogen atom, or a cyano group,with the proviso that, if Ar¹ and Ar^(1′) are a group of formula

and a and d are both 1 and Ar² and Ar^(2′) are different from a group offormula

with the proviso that, if Ar¹ and Ar^(1′) are a group of formula

a and d are not 0;and with the proviso, that a polymer of the formula

is excluded.

The polymers, wherein R¹ and/or R² are hydrogen can be obtained by usinga protecting group which can be removed after polymerization (see, forexample, EP-A-0 648 770, EP-A-0 648 817, EP-A-0 742 255, EP-A-0 761 772,WO98/32802, WO98/45757, WO98/58027, WO99/01511, WO00/17275, WO00/39221,WO00/63297 and EP-A-1 086 984). Conversion of the pigment precursor intoits pigmentary form is carried out by means of fragmentation under knownconditions, for example thermally, optionally in the presence of anadditional catalyst, for example the catalysts described in WO00/36210.

An example of such a protecting group is group of formula

wherein L is any desired group suitable for imparting solubility.

L is preferably a group of formula

wherein Y¹, Y² and Y³ are independently of each other C₁-C₆alkyl,Y⁴ and Y⁸ are independently of each other C₁-C₆alkyl, C₁-C₆alkylinterrupted by oxygen, sulfur or N(Y¹²)₂, or unsubstituted orC₁-C₆alkyl-, C₁-C₆alkoxy-, halo-, cyano- or nitro-substituted phenyl orbiphenyl,Y⁵, Y⁶ and Y⁷ are independently of each other hydrogen or C₁-C₆alkyl,Y⁹ is hydrogen, C₁-C₆alkyl or a group of formula

Y¹⁰ and Y¹¹ are each independently of the other hydrogen, C₁-C₆alkyl,C₁-C₆alkoxy, halogen, cyano, nitro, N(Y¹²)₂, or unsubstituted or halo-,cyano-, nitro-, C₁-C₆alkyl- or C₁-C₆alkoxy-substituted phenyl,Y¹² and Y¹³ are C₁-C₆alkyl, Y¹⁴ is hydrogen or C₁-C₆alkyl, and Y¹⁵ ishydrogen, C₁-C₆alkyl, or unsubstituted or C₁-C₆alkyl-substituted phenyl,Q is p,q-C₂-C₆alkylene unsubstituted or mono- or poly-substituted byC₁-C₆alkoxy,C₁-C₆alkylthio or C₂-C₁₂dialkylamino, wherein p and q are differentposition numbers,X is a hetero atom selected from the group consisting of nitrogen,oxygen and sulfur, m being the number 0 when X is oxygen or sulfur and mbeing the number 1 when X is nitrogen, andL¹ and L² are independently of each other unsubstituted or mono- orpoly-C₁-C₁₂alkoxy-, —C₁-C₁₂alkylthio-, —C₂-C₂₄dialkylamino-,—C₆-C₁₂aryloxy-, —C₆-C₁₂arylthio-, —C₇-C₂₄alkylarylamino- or—C₁₂-C₂₄diarylamino-substituted C₁-C₆alkyl or[-(p′,q′-C₂-C₆alkylene)-Z-]_(n)-C₁-C₆alkyl, n′ being a number from 1 to1000, p′ and q′ being different position numbers, each Z independentlyof any others being a hetero atom oxygen, sulfur orC₁-C₁₂alkyl-substituted nitrogen, and it being possible forC₂-C₆alkylene in the repeating [—C₂-C₆alkylene-Z-] units to be the sameor different,and L₁ and L₂ may be saturated or unsaturated from one to ten times, maybe uninterrupted or interrupted at any location by from 1 to 10 groupsselected from the group consisting of —(C═O)— and —C₆H₄—, and may carryno further substituents or from 1 to 10 further substituents selectedfrom the group consisting of halogen, cyano and nitro. Most preferred Lis a group of formula

The polymers of the present invention can be used as charge-transport,semiconducting, el. conducting, photoconducting, light emittingmaterial, surface-modifying material, electrode materials in batteries,alignment layers, or in OFETs, ICs, TFTs, displays, RFITD tags, electro-or photoluminescent devices, backlights of displays, photovoltaic orsensor devices, charge injection layers, Schottky diodes, memory devices(e.g. FeFET), planarising layers, antistatics, conductive substrates orpatterns, photoconductors, or electrophotographic applications(recording).

The polymers of the present invention can comprise one, or more(different) repeating units of formula I, such as, for example,repeating units of formula Ia and Id.

The repeating unit of formula I can have an asymmetric structure, buthas preferably a symmetric structure: a=d; b=e; c=f; Ar¹=Ar^(1′);Ar²=Ar^(2′); Ar³=Ar^(3′); Ar⁴=Ar^(4′).

R¹ and R² may be the same or different and are preferably selected fromhydrogen, a C₁-C₂₅alkyl group, which can optionally be interrupted byone or more oxygen atoms, a C₁-C₂₅perfluoroalkyl group, an allyl group,which can be substituted one to three times with C₁-C₄alkyl; acycloalkyl group, which can be substituted one to three times withC₁-C₈alkyl, C₁-C₈thioalkoxy, or C₁-C₈alkoxy, or a cycloalkyl group,which can be condensed one or two times by phenyl, which can besubstituted one to three times with C₁-C₄-alkyl, halogen, nitro orcyano, an alkenyl group, a cycloalkenyl group, an alkynyl group, ahaloalkyl group, a haloalkenyl group, a haloalkynyl group, a ketone oraldehyde group, an ester group, a carbamoyl group, a ketone group, asilyl group, a siloxanyl group, Ar¹⁰ or —CR⁵R⁶—(CH₂)_(g)—Ar¹⁰, wherein

R⁵ and R⁶ independently from each other stand for hydrogen, fluorine,cyano or C₁-C₄alkyl, which can be substituted by fluorine, chlorine orbromine, or phenyl, which can be substituted one to three times withC₁-C₄alkyl,R¹ and R² are more preferably selected from C₁-C₂₅alkyl, which canoptionally be interrupted by one or more oxygen atoms,C₅-C₁₂-cycloalkyl, especially cyclohexyl, which can be substituted oneto three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, or C₅-C₁₂cycloalkyl,especially cyclohexyl, which can be condensed one or two times byphenyl, which can be substituted one to three times with C₁-C₄alkyl,halogen, nitro or cyano, phenyl or 1- or 2-naphthyl which can besubstituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, orCR⁵R⁶—(CH₂)_(g)Ar¹⁰ wherein R³ and R⁴ stand for hydrogen, Ar¹⁰ standsfor phenyl or 1- or 2-naphthyl, which can be substituted one to threetimes with C₁-C₈alkyl and/or C₁-C₈alkoxy, and g stands for 0 or 1. Analkyl group which is interrupted one or more times by —O— is understoodto be a straight-chain or branched C₂-C₂₅alkyl radical, which may beinterrupted one or more times by —O—, for example one, two or threetimes by —O—, resulting in structural units such as, for example,—(CH₂)₂OCH₃, —(CH₂CH₂O)₂CH₂CH₃, —CH₂—O—CH₃, —CH₂CH₂—O—CH₂CH₃,—CH₂CH₂CH₂—O—CH(CH₃)₂, —[CH₂CH₂O]_(Y1)—CH₃ wherein Y1=1-10,—CH₂—CH(CH₃)—O—CH₂—CH₂CH₃ and —CH₂—CH(CH₃)—O—CH₂—CH₃.

Most preferred R¹ and R² are a C₁-C₂₅alkyl group, especially aC₄-C₂₅alkyl group, such as n-butyl, sec.-butyl, isobutyl, tert.-butyl,n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl,n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, n-decyl,n-undecyl, n-dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,2-hexyldecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl,tetracosyl or pentacosyl, wherein advantageous groups can be representedby formula

wherein m1=n1+4 and m1+n1≦22.

Chiral side chains, such as R¹ and R², can either be homochiral, orracemic, which can influence the morphology of the polymers.

The present invention does not comprise polymers of formula I, wherein

R¹ and R² are independently of each other a C₁-C₂₅alkyl group,especially a C₄-C₁₂alkyl group, which can be interrupted by one or moreoxygen atoms,Ar¹ and Ar^(1′) are a group of formula

wherein R⁶ is hydrogen, C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, and R³² is methyl,Cl, or OMe,a=b=c=f=0; d=e=1;

Ar^(2′) is selected from

whereinR⁶ is hydrogen, C₁-C₁₅alkyl, or C₁-C₁₈alkoxy, andAr^(3′) is selected from

whereinX¹ is a hydrogen atom, or a cyano group.Ar¹ and Ar^(1′) can be different, but are preferably the same and are agroup of formula

especially

andAr², Ar^(2′), Ar³, Ar^(3′), Ar⁴ and Ar^(4′) are independently of eachother a group of formula

whereinp stands for 0, 1, or 2, R³ may be the same or different within onegroup and is selected from C₁-C₂₅alkyl, which may optionally besubstituted by E and/or interrupted by D, or C₁-C₁₈alkoxy, which mayoptionally be substituted by E and/or interrupted by D; R⁴ isC₆-C₂₅alkyl, which may optionally be substituted by E and/or interruptedby D, C₆-C₁₂aryl, such as phenyl, naphthyl, or biphenylyl, which mayoptionally be substituted by G, C₁-C₂₅alkoxy, which may optionally besubstituted by E and/or interrupted by D, or C₇-C₁₅aralkyl, wherein armay optionally be substituted by G,D is —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —NR²⁵—, wherein R²⁵ isC₁-C₁₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, or sec-butyl;E is —OR²⁹; —SR²⁹; —NR²⁵R²⁵; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁵; or —CN;wherein R²⁵, R²⁷, R²⁸ and R²⁹ are independently of each otherC₁-C₁₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C₆-C₁₄ aryl,such as phenyl, naphthyl, or biphenylyl,G has the same preferences as E, or is C₁-C₁₈alkyl, especiallyC₁-C₁₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl.

The units

Ar⁴_(c)Ar³_(b)Ar²_(a)—Ar¹—

and

—Ar^(1′)Ar^(2′)_(d)Ar^(3′)_(e)Ar^(4′)_(f)—

may be different, but are preferably the same and are a group of formula

wherein

indicates the bond to the diketopyrrolopyrrole skeleton, and R⁴ is asdefined above and R^(4′) has the meaning of R⁴.

In another preferred embodiment of the present invention the units

Ar⁴_(c)Ar³_(b)Ar²_(a)—Ar¹—

and

—Ar^(1′)Ar^(2′)_(d)Ar^(3′)_(e)Ar^(4′)_(f)—

may be different,but are preferably the same and are a group of formula

wherein R⁴ is C₆-C₂₅alkyl, which may optionally be interrupted by one ormore oxygen atoms.

In another preferred embodiment of the present invention the polymercomprises repeating units of the formula

wherein a, b, c, d, e, f, R¹, R², Ar¹, Ar^(1′), Ar², Ar^(2′), Ar³,Ar^(3′), Ar⁴ and Ar^(4′) are as defined above,h is 1, andAr⁵ is a group of formula

wherein R⁷ and R^(7′) are as defined above; orthe polymer has the structure of formula

*First Repeating Unit_(q)Branching Unit_(t)*  (III),

wherein the First “Repeating Unit” is a repeating unit of formula I,the “Branching Unit” is a unit having more than two linkage sites, andq and t are integers, wherein q/t is the ratio of the repeating unit offormula I to the “Branching Unit”.

The repeating unit of formula II has advantageously a symmetricstructure: a=d; b=e; c=f; Ar¹=Ar^(1′); Ar²=Ar^(2′); Ar³=Ar^(3′);Ar⁴=Ar^(4′).

The “Branching Unit” is a unit having more than two linkage sites.Examples of branching units are, for example, described in Dendrimersand Other Dendritic Polymers, D. A. Tomalia, J. M. J. Fréchet (Eds),John Wiley & Sons, Ltd. 2002; Star and Hyperbranched Polymers, M. K.Mishra and S. Kobayashi (Eds), Marcel Dekker 2000.

Examples of especially suitable “Branching” Units are shown below:

wherein B and C are independently of each other an optionally condensedaromatic, or heteroaromatic ring, such as

is the bonding to the DPP backbone,especially

wherein R²⁰⁰, R²⁰¹ and R²⁰² are independently of each other H, orC₁-C₂₅alkyl,

s=1, or 2,

such as

such as

such as

The use of a multi-functional unit (“Branching Unit”) results inbranched polymeric materials, as illustrated below (for exemplarypurposes only) for two multi-functional units:

(A is a repeating unit of formula l, o, q, r and t are 0 to 500), or

The “Branching Unit” of formula

and polymers derived therefrom are new and form further aspects of thepresent invention.

In another preferred embodiment of the present invention the polymerscomprise repeating units of the formula

whereinR¹ and R² are independently from each other C₁-C₂₅alkyl, andR³ and R^(3′) are independently from each other C₆-C₂₅alkyl, which mayoptionally be interrupted by one or more oxygen atoms,R⁴ and R^(4′) are independently from each other C₆-C₂₅alkyl, which mayoptionally be interrupted by one or more oxygen atoms, andR⁷ and R^(7′) are independently from each other C₆-C₂₅alkyl, which mayoptionally be interrupted by one or more oxygen atoms.

In another preferred embodiment of the present invention the polymer isa polymer of the formula

whereinR¹ and R² are independently from each other H, or C₁-C₂₅alkyl, andR⁴ is C₆-C₂₆alkyl, which may optionally be interrupted by one or moreoxygen atoms.

In one embodiment, the polymers according to the invention consist onlyof one or more type of repeating units of formula I. In a preferredembodiment, the polymers according to the invention consist of preciselyone type of repeating unit of formula I (homopolymers).

According to the present invention the term “polymer” comprises polymersas well as oligomers, wherein a polymer is a molecule of high relativemolecular mass, the structure of which essentially comprises therepetition of units derived, actually or conceptually, from molecules oflow relative molecular mass and an oligomer is a molecule ofintermediate molecular mass, the structure of which essentiallycomprises a small plurality of units derived, actually or conceptually,from molecules of lower relative molecular mass. A molecule is regardedas having a high relative molecular mass if it has properties which donot vary significantly with the removal of one or a few of the units. Amolecule is regarded as having an intermediate molecular mass if it hasproperties which do vary significantly with the removal of one or a fewof the units.

According to the present invention a homopolymer is a polymer derivedfrom one species of (real, implicit, or hypothetical) monomer. Manypolymers are made by the mutual reaction of complementary monomers.These monomers can readily be visualized as reacting to give an“implicit monomer”, the homopolymerisation of which would give theactual product, which can be regarded as a homopolymer. Some polymersare obtained by chemical modification of other polymers, such that thestructure of the macromolecules that constitute the resulting polymercan be thought of having been formed by the homopolymerisation of ahypothetical monomer.

Accordingly a copolymer is a polymer derived from more than one speciesof monomer, e.g. bipolymer, terpolymer, quaterpolymer, etc.

The oligomers of this invention have a weight average molecular weightof <2,000 Daltons. The polymers of this invention preferably have aweight average molecular weight of 2,000 Daltons or greater, especially2,000 to 2,000,000 Daltons, more preferably 10,000 to 1,000,000 and mostpreferably 10,000 to 750,000 Daltons. Molecular weights are determinedaccording to gel permeation chromatography using polystyrene standards.

In a preferred embodiment the polymers of the present invention arehomopolymers, comprising repeating units of the formula I, which can berepresented by the formula

A  (VII),

wherein A is a repeating unit of formula I. In said aspect the polymercomprises preferably one of the repeating units of formula Ia to II,wherein repeating units of the formula Ie, Id, Ih and Ii are especiallypreferred.

Copolymers of formula VII, involving repeating units of formula I andCOM¹ or COM² (v=0.995 to 0.005, w=0.005 to 0.995), can also be obtainedby coupling reactions, such as nickel coupling reactions:

*A_(v)* *COM¹_(w)*(VIIa)

or

*A_(v)* *COM²_(w)*  (VIIb),

wherein A is as defined above and -COM¹- is selected from repeatingunits of formula:

wherein R⁷ and R^(7′) are as defined above,R⁴⁴ and R⁴¹ are hydrogen, C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, andR⁴⁵ is H, C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D, especially C₁-C₁₈alkyl which is interrupted by —O—,wherein D and E are as defined above, and -COM²- is a group of formula

whereinR¹¹⁶ and R¹¹⁷ are independently of each other H, C₁-C₁₈alkyl, which canoptionally be interrupted by O, or C₁-C₁₈alkoxy, which can optionally beinterrupted by O,R¹¹⁹ and R¹²⁰ are independently of each other H, C₁-C₁₈alkyl, which canoptionally be interrupted by O, orR¹¹⁹ and R¹²⁰ together form a group of formula ═CR¹⁰⁰R¹⁰¹, whereinR¹⁰⁰ and R¹⁰¹ are independently of each other H, C₁-C₁₈alkyl, orR¹¹⁹ and R¹²⁰ together form a five or six membered ring, whichoptionally can be substituted by C₁-C₁₈alkyl.

In said embodiment the polymer is a polymer of formula

*A_(o)* *COM²_(p)_(q)* *COM¹_(r)* *COM²_(s)_(t)*  (VIIc)

whereinA, COM¹ and COM² are as defined above,o is 1,p is 0, or 1,q is 0.005 to 1,r is 0, or 1,s is 0, or 1, wherein e is not 1, if d is 0,t is 0.995 to 0, wherein the sum of c and f is 1.

Homopolymers of formula VII are, for example, obtained by nickelcoupling reactions, especially the Yamamoto reaction:

A  (VII),

wherein A is a repeating unit of formula I.

Polymerization processes involving only dihalo-functional reactants maybe carried out using nickel coupling reactions. One such couplingreaction was described by Colon et al. in J. Pol. Sci., Part A, PolymerChemistry Edition 28 (1990) 367, and by Colon et al. in J. Org. Chem. 51(1986) 2627. The reaction is typically conducted in a polar aproticsolvent (e.g., dimethylacetamide) with a catalytic amount of nickelsalt, a substantial amount of triphenylphosphine and a large excess ofzinc dust. A variant of this process is described by Ioyda et al. inBull. Chem. Soc. Jpn, 63 (1990) 80 wherein an organo-soluble iodide wasused as an accelerator.

Another nickel-coupling reaction was disclosed by Yamamoto in Progressin Polymer Science 17 (1992) 1153 wherein a mixture of dihaloaromaticcompounds were treated with an excess amount of nickel(1,5-cyclooctadiene) complex in an inert solvent. All nickel-couplingreactions when applied to reactant mixtures of two or more aromaticdihalides yield essentially random copolymers. Such polymerizationreactions may be terminated by the addition of small amounts of water tothe polymerization reaction mixture, which will replace the terminalhalogen groups with hydrogen groups. Alternatively, a monofunctionalaryl halide may be used as a chain-terminator in such reactions, whichwill result in the formation of a terminal aryl group.

Nickel-coupling polymerizations yield essentially homopolymers or randomcopolymers comprising DPP group-containing units and units derived fromother co-monomers.

Homopolymers of formula VIId, or VIIe can be obtained, for example, bythe Suzuki reaction:

A-COM¹  (VIId)

or

A-COM²  (VIIe),

wherein A, COM¹ and COM² are as defined above. Examples of preferredhomopolymers of formula VIId, or VIIe are shown below:

Another example of a homopolymer of formula VIId is the polymer of theformula

whereinR¹ and R² are independently from each other H, or C₁-C₂₅alkyl, andR⁴ is C₆-C₂₅alkyl, which may optionally be interrupted by one or moreoxygen atoms.

The condensation reaction of an aromatic boronate and a halogenide,especially a bromide, commonly referred to as the “Suzuki reaction”, istolerant of the presence of a variety of organic functional groups asreported by N. Miyaura and A. Suzuki in Chemical Reviews, Vol. 95, pp.457-2483 (1995). Preferred catalysts are2-dicyclohexylphosphino-2′,6′-di-alkoxybiphenyl/palladium(11)acetates.An especially preferred catalyst is2-dicyclohexylphosphino-2′,6′-di-methoxybiphenyl(sPhos)/palladium(II)acetate. This reaction can be applied to preparinghigh molecular weight polymers and copolymers.

To prepare polymers corresponding to formula VIId, or VIIe adihalogenide, such as a dibromide or dichloride, especially a dibromidecorresponding to formula

Br-A-Br

is reacted with an equimolar amount of a diboronic acid or diboronatecorresponding to formula

X¹¹COM¹X¹¹,

or

X¹¹COM²X¹¹,

wherein X¹¹ is independently in each occurrence —B(OH)₂, —B(OY¹)₂ or

wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group andY² is independently in each occurrence a C₂-C₁₀alkylene group, such asCY³Y⁴—CY⁵Y⁶—, or CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸,Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or aC₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, or —C(CH₃)₂CH₂C(CH₃)₂—,under the catalytic action of Pd and triphenylphosphine. The reaction istypically conducted at about 70° C. to 180° C. in an aromatichydrocarbon solvent such as toluene. Other solvents such asdimethylformamide and tetrahydrofuran can also be used alone, or inmixtures with an aromatic hydrocarbon. An aqueous base, preferablysodium carbonate or bicarbonate, is used as the HBr scavenger. Dependingon the reactivities of the reactants, a polymerization reaction may take2 to 100 hours. Organic bases, such as, for example, tetraalkylammoniumhydroxide, and phase transfer catalysts, such as, for example TBAB, canpromote the activity of the boron (see, for example, Leadbeater & Marco;Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein).Other variations of reaction conditions are given by T. I. Wallow and B.M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M.Schulze, and G. Wegner in Macromol. Rapid Commun. 17 (1996) 239-252.

If desired, a monofunctional aryl halide or aryl boronate may be used asa chain-terminator in such reactions, which will result in the formationof a terminal aryl group.

It is possible to control the sequencing of the monomeric units in theresulting copolymer by controlling the order and composition of monomerfeeds in the Suzuki reaction.

The polymers of the present invention can also be sythesized by theStille coupling (see, for example, Babudri et al, J. Mater. Chem., 2004,14, 11-34; J. K. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508). Toprepare polymers corresponding to formula VIId, or VIIe a dihalogenide,such as a dibromide or dichloride, especially a dibromide correspondingto formula

Br-A-Br

is reacted with a compound of formula

X¹¹COM¹X¹¹,

or

X¹¹COM²X¹¹,

wherein X¹¹ is a group —SnR²⁰⁷R²⁰⁸R²⁰⁹, in an inert solvent at atemperature in range from 0° C. to 200° C. in the presence of apalladium-containing catalyst. It must be ensured here that the totalityof all monomers used has a highly balanced ratio of organotin functionsto halogen functions. In addition, it may prove advantageous to removeany excess reactive groups at the end of the reaction by end-cappingwith monofunctional reagents. In order to carry out the process, the tincompounds and the halogen compounds are preferably introduced into oneor more inert organic solvents and stirred at a temperature of from 0 to200° C., preferably from 30 to 170° C. for a period of from 1 hour to200 hours, preferably from 5 hours to 150 hours. The crude product canbe purified by methods known to the person skilled in the art andappropriate for the respective polymer, for example repeatedre-precipitation or even by dialysis.

Suitable organic solvents for the process described are, for example,ethers, for example diethyl ether, dimethoxyethane, diethylene glycoldimethyl ether, tetrahydrofuran, dioxane, dioxolane, diisopropyl etherand tert-butyl methyl ether, hydrocarbons, for example hexane,isohexane, heptane, cyclohexane, benzene, toluene and xylene, alcohols,for example methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol,1-butanol, 2-butanol and tert-butanol, ketones, for example acetone,ethyl methyl ketone and isobutyl methyl ketone, amides, for exampledimethylformamide (DMF), dimethylacetamide and N-methylpyrrolidone,nitriles, for example acetonitrile, propionitrile and butyronitrile, andmixtures thereof.

The palladium and phosphine components should be selected analogously tothe description for the Suzuki variant.

Alternatively, the polymers of the present invention can also besynthesized by the Negishi reaction using zinc reagents (A-(ZnX¹²)₂,wherein X¹² is halogen) and halides or triflates (COM¹-(X¹¹)₂, whereinX¹¹ is halogen or triflate). Reference is, for example, made to E.Negishi et al., Heterocycles 18 (1982) 117-22.

In addition, halogen derivatives of the DPPs can be polymerizedoxidatively (for example using FeCl₃, see, inter alia, P. Kovacic etal., Chem. Ber. 87 (1987) 357 to 379; M. Wenda et al., Macromolecules 25(1992) 5125) or electrochemically (see, inter alia, N. Saito et al.,Polym. Bull. 30 (1993) 285).

The monomers of the formula

are new and form a further aspect of the present invention,Wherein B and C are independently of each other an optionally condensedaromatic, or heteroaromatic ring,a, b, c, d, e, f, Ar¹, Ar^(1′), Ar², Ar^(2′), Ar³, Ar^(3′), Ar⁴ andAr^(4′) are as defined in claim 1 and X is ZnX¹², —SnR²⁰⁷R²⁰⁸R²⁰⁹,wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and are H orC₁-C₆alkyl, wherein two radicals optionally form a common ring and theseradicals are optionally branched or unbranched and X¹² is a halogenatom, very especially I, or Br; or —OS(O)₂CF₃, —OS(O)₂-aryl, especially

—OS(O)₂CH₃, —B(OH)₂, —B(OY¹)₂,

—BF₄Na, or —BF₄K, wherein Y¹ is independently in each occurrence aC₁-C₁₀alkyl group and Y² is independently in each occurrence aC₂-C₁₀alkylene group, such as —CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—,wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independentlyof each other hydrogen, or a C₁-C₁₀alkyl group, especially—C(CH₃)₂C(CH₃)₂—, or —C(CH₃)₂CH₂C(CH₃)₂—with the proviso that, if Ar¹ and Ar^(1′) are a group of formula

a and d are not 0 and Ar² and Ar^(2′) are different from a group offormula

with the further proviso that, if Ar¹ and Ar^(1′) are a group of formula

a and d are not 0.

A further aspect of the invention relates to both the oxidised andreduced form of the polymers and materials according to this invention.Either loss or gain of electrons results in formation of a highlydelocalised ionic form, which is of high conductivity. This can occur onexposure to common dopants. Suitable dopants and methods of doping areknown to those skilled in the art, e. g., from EP0528662, U.S. Pat. No.5,198,153, or WO 96/21659.

The doping process typically implies treatment of the semiconductormaterial with an oxidating or reducing agent in a redox reaction to formdelocalised ionic centres in the material, with the correspondingcounterions derived from the applied dopants. Suitable doping methodscomprise for example exposure to a doping vapor in the atmosphericpressure or at a reduced pressure, electrochemical doping in a solutioncontaining a dopant, bringing a dopant into contact with thesemiconductor material to be thermally diffused, and ion-implantantionof the dopant into the semiconductor material.

When electrons are used as carriers, suitable dopants are for examplehalogens (e. g., I₂, Cl₂, Br₂, ICl, ICl₃, IBr and IF), Lewis acids(e.g., PF₅, AsF₅, SbF₅, BF₃, BCl₃, SbCl₅, BBr₃ and S0₃), protonic acids,organic acids, or amino acids (e. g., HF, HCl, HNO₃, H₂SO₄, HClO₄, FSO₃Hand ClSO₃H), transition metal compounds (e.g., FeCl₃, FeOCl, Fe(ClO₄)₃,Fe(4—CH₃C₆H₄SO₃)₃, TiCl₄, ZrCl₄, HfCl₄, NbF₅, NbCl₅, TaCl₅, MoF₅, MoCl₅,WF₅, WCl₆, UF₆ and LnCl₃ (wherein Ln is a lanthanoid), anions (e. g.,Cl⁻, Br⁻, I⁻, I³⁻, HSO₄ ⁻, SO²⁻, NO³⁻, ClO⁴⁻, BF⁴⁻, PF⁶⁻, AsF⁶⁻, SbF⁶⁻,FeCl⁴⁻, Fe(CN)₆ ³⁻, anions of various sulfonic acids, such as aryl —SO₃⁻).

When holes are used as carriers, examples of dopants are cations (e.g.,H⁺, Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺), alkali metals (e.g., Li, Na, K, Rb, andCs), alkaline-earth metals (e.g., Ca, Sr, and Ba), O₂, XeOF₄, (NO₂⁺)(SbF₆ ⁻), (NO₂ ⁺) (SbCl₆ ⁻), (NO₂ ⁺) (BF₄ ⁻), AgClO₄, H₂IrCl₆,La(NO₃)₃.6 H₂O, FSO₂OOSO₂F, Eu, acetylcholine, R₄N⁺, (R is an alkylgroup), R₄P⁺ (R is an alkyl group), R₆As⁺ (R is an alkyl group), andR₃S⁺ (R is an alkyl group).

The conducting form of the compounds and materials of the presentinvention can be used as an organic “metal” in applications, forexample, but not limited to, charge injection layers and ITO planarisinglayers in organic light emitting diode applications, films for flatpanel displays and touch screens, antistatic films, printed conductivesubstrates, patterns or tracts in electronic applications such asprinted circuit boards and condensers.

Halogen is fluorine, chlorine, bromine and iodine.

C₁-C₂₅alkyl is typically linear or branched, where possible. Examplesare methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl,tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl,1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl,1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl.C₁-C₈alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl,sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl,2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl. C₁-C₄alkyl is typicallymethyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl,tert.-butyl.

C₁-C₂₅alkoxy groups are straight-chain or branched alkoxy groups, e.g.methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy,isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy,pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy. Examples ofC₁-C₈alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy,2,2-dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy,1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferably C₁-C₄alkoxy suchas typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec.-butoxy, isobutoxy, tert.-butoxy. The term “alkylthio group” meansthe same groups as the alkoxy groups, except that the oxygen atom of theether linkage is replaced by a sulfur atom.

C₂-C₂₅alkenyl groups are straight-chain or branched alkenyl groups, suchas e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl,isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl,n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.

C₂₋₂₄ alkynyl is straight-chain or branched and preferably C₂₋₈alkynyl,which may be unsubstituted or substituted, such as, for example,ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl,2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl,1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl,trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl,1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.

The terms “haloalkyl, haloalkenyl and haloalkynyl” mean groups given bypartially or wholly substituting the above-mentioned alkyl group,alkenyl group and alkynyl group with halogen, such as trifluoromethyletc. The “aldehyde group, ketone group, ester group, carbamoyl group andamino group” include those substituted by an alkyl group, a cycloalkylgroup, an aryl group, an aralkyl group or a heterocyclic group, whereinthe alkyl group, the cycloalkyl group, the aryl group, the aralkyl groupand the heterocyclic group may be unsubstituted or substituted. The term“silyl group” means a group of formula —SiR⁶²R⁶³R⁶⁴, wherein R⁶², R⁶³and R⁶⁴ are independently of each other a C₁-C₈alkyl group, inparticular a C₁-C₄ alkyl group, a C₆-C₂₄aryl group or a C₇-C₁₂aralkylgroup, such as a trimethylsilyl group. The term “cycloalkyl group” istypically C₅-C₁₂cycloalkyl, such as cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl,cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, orcyclooctyl, which may be unsubstituted or substituted. The term“cycloalkenyl group” means an unsaturated alicyclic hydrocarbon groupcontaining one or more double bonds, such as cyclopentenyl,cyclopentadienyl, cyclohexenyl and the like, which may be unsubstitutedor substituted. The cycloalkyl group, in particular a cyclohexyl group,can be condensed one or two times by phenyl which can be substituted oneto three times with C₁-C₄-alkyl, halogen and cyano. Examples of suchcondensed cyclohexyl groups are:

in particular

wherein R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵ and R⁵⁶ are independently of each otherC₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano, in particular hydrogen.

The term “aryl group” is typically C₆-C₂₄aryl, such as phenyl, indenyl,azulenyl, naphthyl, biphenyl, as-indacenyl, s-indacenyl,acenaphthylenyl, fluorenyl, phenanthryl, fluoranthenyl, triphenlenyl,chrysenyl, naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl,pyrenyl, or anthracenyl, preferably phenyl, 1-naphthyl, 2-naphthyl,4-biphenyl, 9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, whichmay be unsubstituted or substituted. Examples of C₆-C₁₂aryl are phenyl,1-naphthyl, 2-naphthyl, 3- or 4-biphenyl, 2- or 9-fluorenyl or9-phenanthryl, which may be unsubstituted or substituted.

The term “aralkyl group” is typically C₇-C₂₄aralkyl, such as benzyl,2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl,ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl,ω-phenyl-eicosyl or ω-phenyl-docosyl, preferably C₇-C₁₈aralkyl such asbenzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl,ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl orω-phenyl-octadecyl, and particularly preferred C₇-C₁₂aralkyl such asbenzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl,ω-phenyl-butyl, or ω,ω-dimethyl-ω-phenyl-butyl, in which both thealiphatic hydrocarbon group and aromatic hydrocarbon group may beunsubstituted or substituted.

The term “aryl ether group” is typically a C₆₋₂₄aryloxy group, that isto say O—C₆₋₂₄aryl, such as, for example, phenoxy or 4-methoxyphenyl.The term “aryl thioether group” is typically a C₆₋₂₄arylthio group, thatis to say S—C₆₋₂₄aryl, such as, for example, phenylthio or4-methoxyphenylthio. The term “carbamoyl group” is typically aC₁₋₁₈carbamoyl radical, preferably C₁₋₁₈carbamoyl radical, which may beunsubstituted or substituted, such as, for example, carbamoyl,methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl,dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.

The terms “aryl” and “alkyl” in alkylamino groups, dialkylamino groups,alkylarylamino groups, arylamino groups and diarylgroups are typicallyC₁-C₂₅alkyl and C₆-C₂₄aryl, respectively.

Alkylaryl refers to alkyl-substituted aryl radicals, especiallyC₇-C₁₂alkylaryl. Examples are tolyl, such as 3-methyl-, or4-methylphenyl, or xylyl, such as 3,4-dimethylphenyl, or3,5-dimethylphenyl.

Heteroaryl is typically C₂-C₂₆heteroaryl, i.e. a ring with five to sevenring atoms or a condensed ring system, wherein nitrogen, oxygen orsulfur are the possible hetero atoms, and is typically an unsaturatedheterocyclic group with five to 30 atoms having at least six conjugatedπ-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl,thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl,isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl,pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl,pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl,quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl,chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl,carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl,pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl,isoxazolyl, furazanyl or phenoxazinyl, which can be unsubstituted orsubstituted.

Possible substituents of the above-mentioned groups are C₁-C₈alkyl, ahydroxyl group, a mercapto group, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen,halo-C₁-C₈alkyl, a cyano group, an aldehyde group, a ketone group, acarboxyl group, an ester group, a carbamoyl group, an amino group, anitro group or a silyl group.

As described above, the aforementioned groups may be substituted by Eand/or, if desired, interrupted by D. Interruptions are of coursepossible only in the case of groups containing at least 2 carbon atomsconnected to one another by single bonds; C₆-C₁₈aryl is not interrupted;interrupted arylalkyl or alkylaryl contains the unit D in the alkylmoiety. C₁-C₁₈alkyl substituted by one or more E and/or interrupted byone or more units D is, for example, (CH₂CH₂O)₁₋₉—R^(x), where R^(x) isH or C₁-C₁₀alkyl or C₂-C₁₀alkanoyl (e.g. CO—CH(C₂H₅)C₄H₉),CH₂—CH(OR^(y′))—CH₂—O—R^(y), where R^(y) is C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl, phenyl, C₇-C₁₅phenylalkyl, and R^(y′) embraces thesame definitions as R^(y) or is H;

C₁-C₈alkylene-COO—R^(z), e.g. CH₂COOR_(z), CH(CH₃)COOR^(z),C(CH₃)₂COOR^(z), where R^(z) is H, C₁-C₁₈alkyl, (CH₂CH₂O)₁₋₉—R^(x), andR^(x) embraces the definitions indicated above;

CH₂CH₂—O—CO—CH═CH₂; CH₂CH(OH)CH₂—O—CO—C(CH₃)═CH₂.

The polymers of the invention can be used as the semiconductor layer insemiconductor devices. Accordingly, the present invention also relatesto semiconductor devices, comprising a polymer of the formula I. Thesemiconductor device is especially a diode, an organic field effecttransistor and/or a solar cell, or a device containing a diode and/or anorganic field effect transistor, and/or a solar cell. There are numeroustypes of semiconductor devices. Common to all is the presence of one ormore semiconductor materials. Semiconductor devices have been described,for example, by S. M. Sze in Physics of Semiconductor Devices, 2^(nd)edition, John Wiley and Sons, New York (1981). Such devices includerectifiers, transistors (of which there are many types, including p-n-p,n-p-n, and thin-film transistors), light emitting semiconductor devices(for example, organic light emitting diodes in display applications orbacklight in e.g. liquid crystal displays), photoconductors, currentlimiters, solar cells, thermistors, p-n junctions, field-effect diodes,Schottky diodes, and so forth. In each semiconductor device, thesemiconductor material is combined with one or more metals and/orinsulators to form the device. Semiconductor devices can be prepared ormanufactured by known methods such as, for example, those described byPeter Van Zant in Microchip Fabrication, Fourth Edition, McGraw-Hill,New York (2000). In particular, organic electronic components can bemanufactured as described by D. R. Gamota et al. in Printed Organic andMolecular Electronics, Kluver Academic Publ., Boston, 2004.

A particularly useful type of transistor device, the thin-filmtransistor (TFT), generally includes a gate electrode, a gate dielectricon the gate electrode, a source electrode and a drain electrode adjacentto the gate dielectric, and a semiconductor layer adjacent to the gatedielectric and adjacent to the source and drain electrodes (see, forexample, S. M. Sze, Physics of Semiconductor Devices, 2.sup.nd edition,John Wiley and Sons, page 492, New York (1981)). These components can beassembled in a variety of configurations. More specifically, an organicthin-film transistor (OTFT) has an organic semiconductor layer.Typically, a substrate supports the OTFT during manufacturing, testing,and/or use. Optionally, the substrate can provide an electrical functionfor the OTFT. Useful substrate materials include organic and inorganicmaterials. For example, the substrate can comprise silicon materialsinclusive of various appropriate forms of silicon, inorganic glasses,ceramic foils, polymeric materials (for example, acrylics, polyester,epoxies, polyamides, polycarbonates, polyimides, polyketones,poly(oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene)(sometimes referred to as poly(ether ether ketone) or PEEK),polynorbornenes, polyphenyleneoxides, poly(ethylenenaphthalenedicarboxylate) (PEN), poly(ethylene terephthalate) (PET),poly(phenylene sulfide) (PPS)), filled polymeric materials (for example,fiber-reinforced plastics (FRP)), and coated metallic foils.

The gate electrode can be any useful conductive material. For example,the gate electrode can comprise doped silicon, or a metal, such asaluminum, chromium, gold, silver, nickel, palladium, platinum, tantalum,and titanium. Conductive oxides, such as indium tin oxide, or conductinginks/pastes comprised of carbon black/graphite or colloidal silverdispersions, optionally containing polymer binders can also be used.Conductive polymers also can be used, for example polyaniline orpoly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS). Inaddition, alloys, combinations, and multilayers of these materials canbe useful. In some OTFTs, the same material can provide the gateelectrode function and also provide the support function of thesubstrate. For example, doped silicon can function as the gate electrodeand support the OTFT.

The gate dielectric is generally provided on the gate electrode. Thisgate dielectric electrically insulates the gate electrode from thebalance of the OTFT device. Useful materials for the gate dielectric cancomprise, for example, an inorganic electrically insulating material.

The gate dielectric (insulator) can be a material, such as, an oxide,nitride, or it can be a material selected from the family offerroelectric insulators (e.g. organic materials such as poly(vinylidenefluoride/trifluoroethylene or poly(m-xylylene adipamide)), or it can bean organic polymeric insulator (e.g. poly(methacrylate)s,poly(acrylate)s, polyimides, benzocyclobutenes (BCBs), parylenes,polyvinylalcohol, polyvinylphenol (PVP), polystyrenes, polyester,polycarbonates) as for example described in J. Veres et al. Chem. Mat.2004, 16, 4543 or A. Facchetti et al. Adv. Mat. 2005, 17, 1705. Specificexamples of materials useful for the gate dielectric includestrontiates, tantalates, titanates, zirconates, aluminum oxides, siliconoxides, tantalum oxides, titanium oxides, silicon nitrides, bariumtitanate, barium strontium titanate, barium zirconate titanate, zincselenide, and zinc sulphide, including but not limited toPbZr_(x)Ti_(1-x)O₃ (PZT), Bi₄Ti₃O₁₂, BaMgF₄, Ba(Zr_(1-x)Ti_(x))O₃ (BZT).In addition, alloys, hybride materials (e.g. polysiloxanes ornanoparticle-filled polymers) combinations, and multilayers of thesematerials can be used for the gate dielectric. The thickness of thedielectric layer is, for example, from about 10 to 1000 nm, with a morespecific thickness being about 100 to 500 nm, providing a capacitance inthe range of 0.1-100 nanofarads (nF).

The source electrode and drain electrode are separated from the gateelectrode by the gate dielectric, while the organic semiconductor layercan be over or under the source electrode and drain electrode. Thesource and drain electrodes can be any useful conductive materialfavourably providing a low resistance ohmic contact to the semiconductorlayer. Useful materials include most of those materials described abovefor the gate electrode, for example, aluminum, barium, calcium,chromium, gold, silver, nickel, palladium, platinum, titanium,polyaniline, PEDOT:PSS, other conducting polymers, alloys thereof,combinations thereof, and multilayers thereof. Some of these materialsare appropriate for use with n-type semiconductor materials and othersare appropriate for use with p-type semiconductor materials, as is knownin the art.

The thin film electrodes (that is, the gate electrode, the sourceelectrode, and the drain electrode) can be provided by any useful meanssuch as physical vapor deposition (for example, thermal evaporation orsputtering) or (ink jet) printing methods. The patterning of theseelectrodes can be accomplished by known methods such as shadow masking,additive photolithography, subtractive photolithography, printing,microcontact printing, and pattern coating.

The present invention further provides a thin film transistor devicecomprising

a plurality of electrically conducting gate electrodes disposed on asubstrate;a gate insulator layer disposed on said electrically conducting gateelectrodes;a plurality of sets of electrically conductive source and drainelectrodes disposed on said insulator layer such that each of said setsis in alignment with each of said gate electrodes;an organic semiconductor layer disposed in the channel between sourceand drain electrodes on said insulator layer substantially overlappingsaid gate electrodes; wherein said organic semiconductor layer comprisea polymer of the formula I, or a mixture containing a polymer of formulaI.

The present invention further provides a process for preparing a thinfilm transistor device comprising the steps of:

depositing a plurality of electrically conducting gate electrodes on asubstrate;depositing a gate insulator layer on said electrically conducting gateelectrodes;depositing a plurality of sets of electrically conductive source anddrain electrodes on said layer such that each of said sets is inalignment with each of said gate electrodes;depositing a layer of a polymer of the formula I on said insulator layersuch that said layer of the compound of formula I, or a mixturecontaining a polymer of formula I, substantially overlaps said gateelectrodes; thereby producing the thin film transistor device.

A mixture containing a polymer of formula I results in a semi-conductinglayer comprising a polymer of formula I (typically 5% to 99.9999% byweight, especially 20 to 85% by weight) and at least another material.The other material can be, but is not restricted to a fraction of thesame polymer of formula I with different molecular weight, anotherpolymer of formula I, a semi-conducting polymer, organic smallmolecules, carbon nanotubes, a fullerene derivative, inorganic particles(quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.),conductive particles (Au, Ag etc.), insulator materials like the onesdescribed for the gate dielectric (PET, PS etc.).

For heterojunction solar cells the active layer comprises preferably amixture of a polymer of formula I and a fullerene, such as [60]PCBM(=6,6-phenyl-C61-butyric acid methyl ester), or [70]PCBM, in a weightratio of 1:1 to 1:3.

Any suitable substrate can be used to prepare the thin films of thepolymers of the present invention. Preferably, the substrate used toprepare the above thin films is a metal, silicon, plastic, paper, coatedpaper, fabric, glass or coated glass.

Alternatively, a TFT is fabricated by, for example, by solutiondeposition of a polymer on a highly doped silicon substrate covered witha thermally grown oxide layer followed by vacuum deposition andpatterning of source and drain electrodes.

In yet another approach, a TFT is fabricated by deposition of source anddrain electrodes on a highly doped silicon substrate covered with athermally grown oxide and then solution deposition of the polymer toform a thin film.

The gate electrode could also be a patterned metal gate electrode on asubstrate or a conducting material such as, a conducting polymer, whichis then coated with an insulator applied either by solution coating orby vacuum deposition on the patterned gate electrodes.

Any suitable solvent can be used to dissolve, and/or disperse thepolymers of the present application, provided it is inert and can beremoved partly, or completely from the substrate by conventional dryingmeans (e.g. application of heat, reduced pressure, airflow etc.).Suitable organic solvents for processing the semiconductors of theinvention include, but are not limited to, aromatic or aliphatichydrocarbons, halogenated such as chlorinated or fluorinatedhydrocarbons, esters, ethers amides, such as chloroform,tetrachloroethane, toluene, tetraline, anisole, xylene, ethyl acetate,methyl ethyl ketone, dimethyl formamide, dichlorobenzene,trichlorobenzene, propylene glycol monomethyl ether acetate (PGMEA) andmixtures thereof. The solution, and/or dispersion is then applied by amethod, such as, spin-coating, dip-coating, screen printing,microcontact printing, doctor blading or other solution applicationtechniques known in the art on the substrate to obtain thin films of thesemiconducting material.

The term “dispersion” covers any composition comprising thesemiconductor material of the present invention, which is not fullydissolved in a solvent. The dispersion can be done selecting acomposition including at least a polymer of formula I, or a mixturecontaining a polymer of formula I, and a solvent, wherein the polymerexhibits lower solubility in the solvent at room temperature butexhibits greater solubility in the solvent at an elevated temperature,wherein the composition gels when the elevated temperature is lowered toa first lower temperature without agitation;

-   -   dissolving at the elevated temperature at least a portion of the        polymer in the solvent; lowering the temperature of the        composition from the elevated temperature to the first lower        temperature; agitating the composition to disrupt any gelling,        wherein the agitating commences at any time prior to,        simultaneous with, or subsequent to the lowering the elevated        temperature of the composition to the first lower temperature;        depositing a layer of the composition wherein the composition is        at a second lower temperature lower than the elevated        temperature; and drying at least partially the layer.

The dispersion can also be constituted of (a) a continuous phasecomprising a solvent, a binder resin, and optionally a dispersing agent,and (b) a disperse phase comprising a polymer of formula I, or a mixturecontaining a polymer of formula I of the present invention.

The degree of solubility of the polymer of formula I in the solvent mayvary for example from 0% to about 20% solubility, particularly from 0%to about 5% solubility.

Preferably, the thickness of the organic semiconductor layer is in therange of from about 5 to about 1000 nm, especially the thickness is inthe range of from about 10 to about 100 nm.

The polymers of the invention can be used alone or in combination as theorganic semiconductor layer of the semiconductor device. The layer canbe provided by any useful means, such as, for example, vapor deposition(for materials with relatively low molecular weight) and printingtechniques. The compounds of the invention may be sufficiently solublein organic solvents and can be solution deposited and patterned (forexample, by spin coating, dip coating, ink jet printing, gravureprinting, flexo printing, offset printing, screen printing, microcontact(wave)-printing, drop or zone casting, or other known techniques).

The polymers of the invention can be used in integrated circuitscomprising a plurality of OTFTs, as well as in various electronicarticles. Such articles include, for example, radio-frequencyidentification (RFID) tags, backplanes for flexible displays (for usein, for example, personal computers, cell phones, or handheld devices),smart cards, memory devices, sensors (e.g. light-, image-, bio-, chemo-,mechanical- or temperature sensors), especially photodiodes, or securitydevices and the like. Due to its ambi-polarity the material can also beused in Organic Light Emitting Transistors (OLET).

The invention provides organic photovoltaic (PV) devices (solar cells)comprising a polymer according to the present invention.

The PV device comprise in this order:

(a) a cathode (electrode),(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,(c) a photoactive layer,(d) optionally a smoothing layer,(e) an anode (electrode),(f) a substrate.

The photoactive layer comprises the polymers of the present invention.Preferably, the photoactive layer is made of a conjugated polymer of thepresent invention, as an electron donor and an acceptor material, like afullerene, particularly a functionalized fullerene PCBM, as an electronacceptor.

The fullerenes useful in this invention may have a broad range of sizes(number of carbon atoms per molecule). The term fullerene as used hereinincludes various cage-like molecules of pure carbon, includingBuckminsterfullerene (C₆₀) and the related “spherical” fullerenes aswell as carbon nanotubes. Fullerenes may be selected from those known inthe art ranging from, for example, C₂₀-C₁₀₀₀. Preferably, the fullereneis selected from the range of C₆₀ to C₉₆. Most preferably the fullereneis C₆₀ or C₇₀, such as [60]PCBM, or [70]PCBM. It is also permissible toutilize chemically modified fullerenes, provided that the modifiedfullerene retains acceptor-type and electron mobility characteristics.The acceptor material can also be a material selected from the groupconsisting of another polymer of formula I or any semi-conductingpolymer provided that the polymers retain acceptor-type and electronmobility characteristics, organic small molecules, carbon nanotubes,inorganic particles (quantum dots, quantum rods, quantum tripods, TiO₂,ZnO etc.).

The electrodes are preferably composed of metals or “metal substitutes”.Herein the term “metal” is used to embrace both materials composed of anelementally pure metal, e.g., Mg, and also metal alloys which arematerials composed of two or more elementally pure metals, e.g., Mg andAg together, denoted Mg:Ag. Here, the term “metal substitute” refers toa material that is not a metal within the normal definition, but whichhas the metal-like properties that are desired in certain appropriateapplications. Commonly used metal substitutes for electrodes and chargetransfer layers would include doped wide-bandgap semiconductors, forexample, transparent conducting oxides such as indium tin oxide (ITO),gallium indium tin oxide (GITO), and zinc indium tin oxide (ZITO).Another suitable metal substitute is the transparent conductive polymerpolyanaline (PANI) and its chemical relatives, or PEDOT:PSS. Metalsubstitutes may be further selected from a wide range of non-metallicmaterials, wherein the term “non-metallic” is meant to embrace a widerange of materials provided that the material is free of metal in itschemically uncombined form. Highly transparent, non-metallic, lowresistance cathodes or highly efficient, low resistancemetallic/non-metallic compound cathodes are, for example, disclosed inU.S. Pat. No. 6,420,031 and U.S. Pat. No. 5,703,436.

The substrate can be, for example, a plastic (flexible substrate), orglass substrate.

In another preferred embodiment of the invention, a smoothing layer issituated between the anode and the photoactive layer. A preferredmaterial for this smoothing layer comprises a film of3,4-polyethylenedioxythiophene (PEDOT), or3,4-polyethylenedioxythiophene:polystyrene-sulfonate (PEDOT:PSS).

In a preferred embodiment of the present invention, the photovoltaiccell comprises, as described for example, in U.S. Pat. No. 6,933,436 atransparent glass carrier, onto which an electrode layer made ofindium/tin oxide (ITO) is applied. This electrode layer generally has acomparatively rough surface structure, so that it is covered with asmoothing layer made of a polymer, typically PEDOT, which is madeelectrically conductive through doping. The photoactive layer is made oftwo components, has a layer thickness of, for example, 100 nm to a fewμm depending on the application method, and is applied onto thissmoothing layer. Photoactive layer is made of a conjugated polymer ofthe present invention, as an electron donor and a fullerene,particularly functionalized fullerene PCBM, as an electron acceptor.These two components are mixed with a solvent and applied as a solutiononto the smoothing layer by, for example, the spin-coating method, thecasting method, the Langmuir-Blodgett (“LB”) method, the ink jetprinting method and the dripping method. A squeegee or printing methodcould also be used to coat larger surfaces with such a photoactivelayer. Instead of toluene, which is typical, a dispersion agent such aschlorobenzene is preferably used as a solvent. Among these methods, thevacuum deposition method, the spin-coating method, the ink jet printingmethod and the casting method are particularly preferred in view of easeof operation and cost.

In the case of forming the layer by using the spin-coating method, thecasting method and ink jet printing method, the coating can be carriedout using a solution and/or dispersion prepared by dissolving, ordispersing the composition in a concentration of from 0.01 to 90% byweight in an appropriate organic solvent such as benzene, toluene,xylene, tetrahydrofurane, methyltetrahydrofurane, N,N-dimethylformamide,acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide,chlorobenzene, 1,2-dichlorobenzene and mixtures thereof.

Before a counter electrode is applied, a thin transition layer, whichmust be electrically insulating, having a layer thickness of, forexample, 0.6 nm, is applied to photoactive layer 4. In this exemplaryembodiment, this transition layer is made of an alkali halogenide,namely a lithium fluoride, which is vapor deposited in a vacuum of2·10⁻⁶ torr at a rate of 0.2 nm/minute.

If ITO is used as a hole-collecting electrode, aluminum, which is vapordeposited onto the electrically insulating transition layer, is used asan electron-collecting electrode. The electric insulation properties ofthe transition layer obviously prevent influences which hinder thecrossing of the charge carrier from being effective, particularly in thetransition region from the photoactive layer to the transition layer.

In a further embodiment on the invention, one or more of the layers maybe treated with plasma prior to depositing the next layer. It isparticularly advantageous that the PEDOT:PSS layer be subject to a mildplasma treatment prior to deposition of the next layer.

The photovoltaic (PV) device can also consist of multiple junction solarcells that are processed on top of each other in order to absorb more ofthe solar spectrum. Such structures are, for example, described in App.Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006)and WO2004/112161.

A so called ‘tandem solar cell’ comprise in this order:

(a) a cathode (electrode),(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,(c) a photoactive layer,(d) optionally a smoothing layer,(e) a middle electrode (such as Au, Al, ZnO, TiO₂ etc.)(f) optionally an extra electrode to match the energy level,(g) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,(h) a photoactive layer,(i) optionally a smoothing layer,(j) an anode (electrode),(k) a substrate.

The PV device can also be processed on a fiber as described, forexample, in US20070079867 and US 20060013549.

Due to their excellent self-organising properties the inventivecompounds, materials or films can also be used alone or together withother materials in or as alignment layers in LCD or OLED devices, asdescribed for example in US2003/0021913.

The following examples are included for illustrative purposes only anddo not limit the scope of the claims. Unless otherwise stated, all partsand percentages are by weight. Weight-average molecular weight (M_(w))and polydispersity (M_(w)/M_(n)=PD) are determined by Gel PermeationChromatography (GPC) [Apparatus: GPC_(max)+TDA 302 from Viscotek(Houston, Tex., USA) yielding the responses form refractive index (RI),low angle light scattering (LALS), right angle light scattering (RALS)and differential viscosity (DP) measurements. Chromatographicconditions: Column: PL_(gel) mixed C (300×7.5 mm, 5 μm particles)covering the molecular weight range from about 1×10³ to about 2.5×10⁶ Dafrom Polymer Laboratories (Church Stretton, UK); Mobile phase:tetrahydrofuran containing 5 g/l of sodium trifluoroacetate; Mobilephase flow: either 0.5 or 0.7 ml/min; Solute concentration: about 1-2mg/ml; Injection volume: 100 μl; Detection: RI, LALS, RALS, DP.Procedure of molecular weight calibration: Relative calibration is doneby use of a set of 10 polystyrene calibration standards obtained fromPolymer Laboratories (Church Stretton, UK) spanning the molecular weightrange from 1'930'000 Da-5'050 Da, i. e., PS 1'930'000, PS 1'460'000, PS1'075'000, PS 560'000, PS 330'000, PS 96'000, PS 52'000, PS 30'300, PS10'100, PS 5'050 Da. Absolute calibration is done on the base of theresponses of LALS, RALS and DP. As experienced in a large number ofinvestigations this combination provides optimum calculation ofmolecular weight data. Usually PS 96'000 is used as the molecular weightcalibration standard, but in general every other PS standard lying inthe molecular weight range to be determined can be chosen for thispurpose.

All polymer structures given in the examples below are idealizedrepresentations of the polymer products obtained via the polymerizationprocedures described. If more than two components are copolymerized witheach other sequences in the polymers can be either alternating or randomdepending on the polymerisation conditions.

EXAMPLES Example 1

a) A solution of 4.5 g of DPP 1, 6.23 g of K₂CO₃ and 8.68 g of1-bromo-2-ethyl-hexyl in 60 ml of N-methyl-pyrrolidone (NMP) is heatedto 140° C. for 6 h. The mixture is washed with water and extracted withdichloromethane. The organic phase is then dried and filtered on adouble layer of silica gel and Hyflo® (CAS 91053-39-3; Fluka 56678)before it is concentrated. The residue is dissolved in 100 ml ofchloroform, cooled down to 0° C. and 2 equivalents of N-bromosuccinimideare then added portion wise over a period of 1 h. After the reaction hasbeen completed, the mixture is washed with water. The organic phase isextracted, dried and concentrated. The compound is then purified over asilica gel column to give 1.90 g of a violet powder of DPP 2.

b) A solution of 500 mg of the dibrominated DPP 2, 990 mg of the tinderivative and 85 mg of Pd(PPh₃)₄ in 30 ml of dry toluene is refluxedovernight under inert conditions. After cooling down, the mixture isfiltrated on a double layer silica gel/Hyflo®, concentrated andprecipitated with methanol. The precipitate is filtrated and rinsed withmethanol to give 530 mg of a blue solid of DPP 3.

c) A solution of 2.55 g of the corresponding monomer 3 in chlorobenzeneis degassed with argon over 15 min at 50° C. Then 1.6 g of FeCl₃ areadded in nitromethane and the mixture is stirred while degassing for 4hours at 50° C. The solution is then poured into methanol and the blueprecipitate is then filtrated and washed with methanol. The solid isthen purified by soxhlet extraction, using methanol and hexane to purifyand chloroform to extract 2 g of the polymer fraction (4).

M_(w)=13301

Fe content=75 ppm

Photophysical Properties:

UV spectra of spin coated films on glass substrates are made from hotchlorobenzene solutions and annealed at different temperatures:

Annealing Conditions UV/Vis-absorption Room temperature 680 nm 20minutes at 100° C. 720 nm, 800 nm 20 minutes at 150° C. 720 nm, 800 nmGrowing of the band at 800 nm shows the appearance of strong aggregationbehaviour while annealing.

Application Example 1a DPP-Polymers Based Field-Effect Transistors a)Experimental:

Bottom-gate thin-film transistor (TFT) structures with p-Si gate wereused for all experiments. A high-quality thermal SiO₂ layer served asgate-insulator of C_(i)=32.6 nF/cm² capacitance per unit area. Sourceand drain electrodes were patterned by photolithography directly on thegate-oxide (bottom-contact configuration). On each substrate 16transistors are present with Au source/drain electrodes definingchannels of different length. Prior to the deposition of the organicsemiconductor the SiO₂ surface was derivatized with hexamethyldisilazane(HMDS) or octadecyltrichlorosilane (OTS). The films are prepared eitherby spin casting or drop casting the polymer obtained in example 1 indifferent solvents. The transistor behaviour is measured on an automatedtester elaborated by CSEM, Transistor Prober TP-10.

b) Transistor Performance:

The thin-film transistors showed clear p-type transistor behavior. Froma linear fit to the square root of the saturated transfercharacteristics a field-effect mobility of 0.15 cm²/Vs could bedetermined. The transistors showed a threshold voltage of about 0 V to 5V. The transistors showed good on/off current ratios of 10⁴ to 10⁷.

Annealing of the sample results in a drastic increase of theperformances (especially mobility), which can be correlated to a betteraggregation of the polymer in the solid state. Testing of a set of OFETsafter 2 months exposed in air conditions shows remarkable stability asthe mobility is almost constant. The on/off ratio, which usually suffersthe most, is only reduced by a factor of 10.

Application Example 1b DPP-Polymer Based Bulk Heterojunction Solar Cella) Experimental:

The solar cell has the following structure: Al electrode/LiFlayer/organic layer, including polymer of theinvention/[poly(3,4-ethylenedioxy-thiophene)(PEDOT)/poly(styrenesulfonic acid) (PSS)]/ITO electrode/glass substrate.The solar cells are made by spin-coating a layer of PEDOT-PSS on apre-patterned ITO on glass substrate. Then a 1:4 mixture of the polymerof example 1 (0.5% by weight):[60]PCBM (a substituted C₆₀ fullerene:

is spin coated (organic layer). LiF and Al are sublimed under highvacuum through a shadow-mask.

b) Solar Cell Performance:

The solar cell is measured under a solar light simulator. Then with theExternal Quantum Efficiency (EQE) graph the current is estimated underAM1.5 conditions.

This leads to value of J_(sc)=4.1 mA/cm², FF=0.539 and V_(∝)=0.733 V foran estimated overall efficiency of 1.62% measured before annealing.After 10 min at 100° C. the estimated efficiency grows to 2%. Afteroptimisation of the morphology of the active layer by varying thedeposition solvent, the polymer/[60]PCBM ratio etc. the performance ofthe device can be pushed up to 3.06% (J_(sc)=9.5 mA/cm², FF=0.46 andV_(∝)=0.7 V).

Example 2

A solution of 25 g of DPP 1, 46.07 g of K₂CO₃ and 75 g of1-bromo-2-hexyl-decyl in 300 ml of N-methyl-pyrrolidone (NMP) is heatedto 140° C. for 6 h. The mixture is washed with water and extracted withdichloromethane. The organic phase is then dried and filtered on adouble layer of silica gel and Hyflo® before it is concentrated. Theresidue is dissolved in 100 ml of chloroform, cooled down to 0° C. and 2equivalents of N-bromosuccinimide are then added portion wise over aperiod of 1 h. After the reaction has been completed, the mixture iswashed with water. The organic phase is extracted, dried andconcentrated. The compound is then purified over a silica gel column togive 19 g of a violet powder of DPP 5.

b) A solution of 18.5 g of the dibrominated DPP 5, 27.47 g of the tinderivative and 2.36 g of Pd(PPh₃)₄ in 250 ml of dry toluene is refluxedovernight under inert conditions. After cooling down, the mixture ispurified on a silica gel column (CHCl₃/hexane 3/7) to give 20.2 g of ablue solid of DPP 6.

c) A solution of 10 g of the DPP derivative 6 is dissolved in 300 ml ofchloroform, cooled down to 0° C. and 2 equivalents of N-bromosuccinimideare then added portion wise over a period of 1 h. After the reaction iscompleted, the mixture is washed with water. The organic phase isextracted, dried, concentrated and precipitated with methanol. Theprecipitate is filtrated and rinsed with methanol to give 10 g of a bluesolid of DPP 7.

In a shlenk tube, a solution of 240 mg of Ni(COD)₂ and 140 mg bipyridinein 10 ml of toluene is degassed for 15 min. 1 g of the correspondingdibrominated monomer 7 is added to this solution and then the mixture isheated to 80° C. and stirred vigorously overnight. The solution ispoured on 100 ml of a 1/1/1 methanol/HCl/acetone mixture and stirred for1 h. The precipitate is then filtrated, dissolved in CHCl₃ and stirredvigorously at 60° C. with an aqueous solution ofethylenediaminetetraacetic acid (EDTA) tetrasodium salt for oneadditional hour. The organic phase is washed with water, concentratedand precipitated in methanol. The residue is purified by soxhletextraction using methanol and hexane and the polymer is then extractedwith CHCl₃ to give 250 mg of purple fibres.

M_(w)=77465

Ni content=65 ppmSolubility >10% by weight in toluene

Photophysical Properties:

UV of spin coated film on glass substrate is made from a hotchlorobenzene solution and annealed at different temperatures:

Annealing Conditions UV/Vis-absorption Room temperature 680 nm 20minutes at 100° C. 720 nm, 800 nm

Growing of the band at 800 nm shows the appearance of strong aggregationbehaviour while annealing.

Application Example 2a DPP-Polymers Based Field-Effect Transistors a)Experimental:

Application Example 1a is repeated, except that instead of the polymerobtained in example 1 the polymer obtained in example 2 is used.

b) Transistor Performance:

The thin-film transistors showed clear p-type transistor behavior. Froma linear fit to the square root of the saturated transfercharacteristics a field-effect mobility up to 0.013 cm²/Vs could bedetermined. The transistors showed a threshold voltage of about 0 V to 4V. The transistors showed good on/off current ratios of 10⁵ to 10⁷.Testing of a set of OFETs after 7 days exposed in air conditions showsremarkable stability as the mobility is almost constant even better,on/off ratio which usually suffers the most is only reduced by a factorof 5. This compound shows an electron mobility up to 10⁻³ cm²/Vs on thenormal setup. After optimisation of this setup using top contacttransistors, the ambi-polarity of this polymer is even more pronouncedwith similar mobilities for holes and electrons up to 0.1 cm²/Vs.

Example 3

a) A solution of 25 g of DPP 1, 46.07 g of K₂CO₃ and 55 g of1-bromo-2-butyl-hexyl in 300 ml of N-methyl-pyrrolidone (NMP) is heatedto 140° C. for 6 h. The mixture is washed with water and extracted withdichloromethane. The organic phase is then dried and filtered on adouble layer of silica gel and Hyflo® before it is concentrated. Theresidue is dissolved in 100 ml of chloroform, cooled down to 0° C. and 2equivalents of N-bromosuccinimide are then added portion wise over aperiod of 1 h. After the reaction has been completed, the mixture iswashed with water. The organic phase is extracted, dried andconcentrated. The compound is then purified over a silica gel column togive 9.5 g of a violet powder of DPP 8.

b) A solution of 2.24 g of the dibrominated DPP 8, 4.11 g of the tinderivative and 351 mg of Pd(PPh₃)₄ in 50 ml of dry toluene is refluxedovernight under inert conditions. After cooling down, the mixture ispurified on a silica gel column (CHCl₃/hexane 3/7) to give 2.37 g of ablue solid of DPP 9.

c) A solution of 1.27 g of the DPP derivative 9 is dissolved in 60 ml ofchloroform, cooled down to 0° C. and 2 equivalents of N-bromosuccinimideare then added portion wise over a period of 1 h. After the reaction iscompleted, the mixture is washed with water. The organic phase isextracted, dried, concentrated and precipitated with methanol. Theprecipitate is filtrated and rinsed with methanol to give 1.32 g of ablue solid of DPP 10.

d) In a Schlenk tube, a solution of 244 mg of Ni(COD)₂ and 142 mgbipyridine in 10 ml of toluene is degassed for 15 min. 1 g of thecorresponding dibrominated monomer 10 is added to this solution and thenthe mixture is heated to 80° C. and stirred vigorously overnight. Thesolution is poured on 100 ml of a 1/1/1 methanol/HCl/acetone mixture andstirred for 1 h. The precipitate is then filtrated, dissolved in CHCl₃and stirred vigorously at 60° C. with an aqueous solution ofethylenediaminetetraacetic acid (EDTA) tetrasodium salt for oneadditional hour. The organic phase is washed with water, concentratedand precipitated in methanol. The residue is purified by soxhletextraction using methanol and hexane and the polymer is then extractedwith CHCl₃ to give 650 mg of purple fibres.

M_(w)=30000

Ni content=52 ppmSolubility=0.5% by weight in CHCl₃

Photophysical Properties:

UV of spin coated film on glass substrate is made from a hotchlorobenzene solution and annealed at different temperatures:

Annealing Conditions UV/Vis-absorption Room temperature 720 nm, 810 nm

The band at 810 nm is attributed to the aggregation behaviour.

Application Example 3 DPP-Polymers Based Field-Effect Transistors a)Experimental:

Application Example 1a is repeated, except that instead of the polymerobtained in example 1 the polymer obtained in example 3 is used.

b) Transistor Performance:

The thin-film transistors showed clear p-type transistor behaviour. Froma linear fit to the square root of the saturated transfercharacteristics a field-effect mobility up to 0.1 cm²/Vs could bedetermined. The transistors showed a threshold voltage of about 6 V. Thetransistors showed good on/off current ratios of 10⁴ to 105.

Example 4

a) A solution of 3.5 g of DPP 11, 3.04 g of K₂CO₃ and 4.13 g of1-bromo-2-hexyl-decyl in 60 ml of N-methyl-pyrrolidone (NMP) is heatedto 140° C. for 6 h. The mixture is washed with water and extracted withdichloromethane. The organic phase is then dried and filtered on adouble layer of silica gel and Hyflo® before it is concentrated. Theresidue is dissolved in 100 ml of chloroform, cooled down to 0° C. and 2equivalents of N-bromosuccinimide are then added portion wise over aperiod of 1 h. After the reaction has been completed, the mixture iswashed with water. The organic phase is extracted, dried andconcentrated. The compound is then purified over a silica gel column togive 1.7 g of a violet powder of DPP 12.

b) A solution of 1.6 g of the dibrominated DPP 12, 0.65 g of the tinderivative and 150 mg of Pd(PPh₃)₄ in 60 ml of dry toluene is refluxedovernight under inert conditions. After cooling down, the mixture ispurified on a silica gel column (CHCl₃/hexane 3/7) to give 1.27 g of ablue solid of DPP 13.

c) A solution of 1.27 g of the DPP derivative 13 is dissolved in 50 mlof chloroform, cooled down to 0° C. and 2 equivalents ofN-bromosuccinimide are then added portion wise over a period of 1 h.After the reaction is completed, the mixture is washed with water. Theorganic phase is extracted, dried, concentrated and precipitated withmethanol. The precipitate is filtrated and rinsed with methanol to give1.22 g of a blue solid of DPP 14.

d) In a Schlenk tube, a solution of 292 mg of Ni(COD)₂ and 170 mgbipyridine in 10 ml of toluene is degassed for 15 min. 1.2 g of thecorresponding dibrominated monomer 14 is added to this solution and thenthe mixture is heated to 65° C. and stirred vigorously for 41 h. Thesolution is poured on 100 ml of a 1/1/1 methanol/HCl/acetone mixture andstirred for 1 h. The precipitate is then filtrated, dissolved in CHCl₃and stirred vigorously at 60° C. with an aqueous solution ofethylenediaminetetraacetic acid (EDTA) tetrasodium salt for oneadditional hour. The organic phase is washed with water, concentratedand precipitated in methanol. The residue is purified by soxhletextraction using methanol and hexane and the polymer is then extractedwith CHCl₃ to give 730 mg of purple fibres.

M_(w)=30000

Ni content=14 ppmSolubility=0.5% by weight in CHCl₃

Photophysical Properties:

UV of spin coated film on glass substrate is made from a hotchlorobenzene solution and annealed at different temperatures:

Annealing Conditions UV/Vis-absorption Room temperature 720 nm, 800 nm

The band at 800 nm is attributed to the aggregation behaviour.

Application Example 4 DPP-Polymers Based Field-Effect Transistors a)Experimental:

Application Example 1a is repeated, except that instead of the polymerobtained in example 1 the polymer obtained in example 4 is used.

b) Transistor Performance:

The thin-film transistors showed clear p-type transistor behaviour. Froma linear fit to the square root of the saturated transfercharacteristics a field-effect mobility up to 0.013 cm²/Vs could bedetermined. The transistors showed a threshold voltage of about 4 V to 8V. The transistors showed good on/off current ratios of 10⁴ to 10⁵.Testing of a set of OFETs after 2 months exposed in air conditions showsremarkable stability as the mobility is even better (up to 0.028cm²/Vs), on/off ratio which usually suffer the most is also increased bya factor of 5 to 10 and threshold voltage in the range of 0 V to 4 V.

Example 5

In a three neck-flask, a degassed solution of 5 g of 7, 1.185 g of1,4-benzenediboronic acid bis(pinacol) ester, 3.773 g of K₃PO₄, 88.5 mgof sPhos (2-dicyclohexylphosphino-2′,6′-dimethoxyphenybiphenyl) and 80.6mg of palladium acetate in 60 ml of toluene, 20 nil of dioxane and 10 mlof water are heated to 90° C. and stirred vigorously overnight. Anexcess of bromobenzene is then added and after 2 hours at the sametemperature an excess of phenylboronic acid pinacol ester is then addedto end cap the polymer. After 2 hours to complete the end-capping, 100mL of NaCN (1% by weight) in water is added and the mixture is stirredat 90° C. for 3 hours. The organic phase is extracted and precipitatedin methanol. The residue is redissolved in toluene and resubmitted toNaCN treatment and the organic phase is precipitated in methanol. Theresidue is purified by soxhlet extraction using acetone and Et₂O and thepolymer is then extracted with CHCl₃ to give 2.5 g of purple fibres.

M_(w)=27000

Pd content=30 ppmSolubility=1% by weight in CHCl₃

Photophysical Properties:

UV of spin coated film on glass substrate is made from a hotchlorobenzene solution and annealed at different temperatures:

Annealing Conditions UV/Vis-absorption Room temperature 630 nm, 680 nmThe band at 680 nm is attributed to the aggregation behaviour.

Example 6

1 g of 7, 82 mg of Pd(PPh₃)₄ (10 mol %) and 13.5 mg of copper iodide (10mol %) are dissolved in diethylamine, (0.85 ml) and THF (2 ml) in a dry,nitrogen flushed flask. The flask is then set under vacuum, flushed withnitrogen, this is repeated three times. 328 mg of the diacetyleniquederivative is then added, the flask is sealed under nitrogen, heated upto 85° C. and stirred over night. The reaction mixture is dissolved in50 ml CHCl₃, triturated in 500 ml MeOH, and filtrated. This action isrepeated once. The solid is then purified via soxhlet extraction usingMeOH, acetone and heptane and the polymer is then extracted with CHCl₃to give 0.5 g of purple fibres.

M_(w)=38000

Solubility=0.5% by weight in CHCl₃

Photophysical Properties:

UV of spin coated film on glass substrate is made from a hotchlorobenzene solution and annealed at different temperatures:

Annealing Conditions UV/Vis-absorption Room temperature 650 nm, 700 nm

The band at 700 nm is attributed to the aggregation behaviour.

1.-10. (canceled)
 11. A polymer comprising repeating unit(s) of theformula:

wherein a, b, c, d, e and f are each, independently, 0, 1, 2, or 3,wherein Ar¹ and Ar^(1′) are the same and are a group of the formula:

Ar², Ar^(2′), Ar³, Ar^(3′), Ar⁴ and Ar^(4′) are each, independently, agroup of formula:

R⁴ is C₆-C₂₅alkyl, which may optionally be substituted by E and/orinterrupted by D, C₆-C₁₄aryl, which may optionally be substituted by G,C₁-C₂₅alkoxy, which may optionally be substituted by E and/orinterrupted by D, or C₇-C₁₅aralkyl, wherein ar may optionally besubstituted by G, D is —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, or —NR²⁵—,R²⁵ is C₁-C₁₂alkyl, E is OR²⁹, —SR²⁹, —NR²⁵R²⁵, —COR²⁸, —COOR²⁷,—CONR²⁵R²⁵, or —CN, R²⁵, R²⁷, R²⁸ and R²⁹ are each, independently,C₁-C₁₂alkyl or C₆-C₁₄ aryl, and G is E or C₁-C₁₈alkyl R¹ and R², whichmay be the same or different, are hydrogen, a C₁-C₂₅alkyl group, analkenyl group, an alkynyl group, which may optionally be substituted byE and/or interrupted by D, an allyl group, which can be substituted oneto three times with C₁-C₄alkyl, a cycloalkyl group, which can besubstituted one to three times with C₁-C₅alkyl, C₁-C₈thioalkoxy, orC₁-C₈alkoxy, or a cycloalkyl group, which can be condensed one or twotimes by phenyl, which can be substituted one to three times withC₁-C₄-alkyl, halogen, nitro or cyano, a cycloalkenyl group, a ketone oraldehyde group, an ester group, a carbamoyl group, a silyl group, asiloxanyl group, Ar¹⁰ or —CR⁵R⁶—(CH₂)_(g)—Ar¹⁰, R⁵ and R⁶ are each,independently, hydrogen, fluorine, cyano or C₁-C₄alkyl, which can besubstituted by fluorine, chlorine or bromine, or phenyl, which can besubstituted one to three times with C₁-C₄alkyl, Ar¹⁰ is aryl orheteroaryl, which may optionally be substituted by G, and g is 0, 1, 2,3 or 4, with the proviso that, if Ar¹ and Ar^(1′) are a group of theformula

then a and d are not
 0. 12. The polymer according to claim 11, whereinAr⁴_(c)Ar³_(b)Ar²_(a)—Ar¹—and—Ar^(1′)Ar^(2′)_(d)Ar^(3′)_(e)Ar^(4′)_(f)— and may be the same ordifferent, and are a group of formula:

wherein

indicates the bond to the diketopyrrolopyrrole skeleton, and R⁴ isC₆-C₂₅alkyl, which may optionally be substituted by E and/or interruptedby D, C₆-C₁₄aryl, which may optionally be substituted by G,C₁-C₂₅alkoxy, which may optionally be substituted by E and/orinterrupted by D, or C₇-C₁₅aralkyl, wherein ar may optionally besubstituted by G, D is —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, or —NR²⁵—,R²⁵ is C₁-C₁₂alkyl, E is OR²⁹, —SR²⁹, —NR²⁵R²⁵, —COR²⁸, —COOR²⁷,—CONR²⁵R²⁵, or —CN, R²⁵, R²⁷, R²⁸ and R²⁹ are each, independently,C₁-C₁₂alkyl or C₆-C₁₄ aryl, G is E or C₁-C₁₈alkyl, and R^(4′) is R⁴. 13.The polymer according to claim 11, wherein the polymer is a co-polymercomprising repeating units of formula *A_(v)* and *COM¹_(w)*,*A_(v)* and *COM²_(w)*, A-COM¹, or A-COM², wherein A is arepeating unit of formula I as defined in claim 19, v is 0.995 to 0.005,w is 0.005 to 0.995, and -COM¹- is a repeating unit of the formula:

R⁷ and R^(7′) are as defined in claims 19, R⁴⁴ and R⁴¹ are hydrogen,C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, R⁴⁵ is H, C₁-C₁₈alkyl, or C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, wherein D and E areas defined in claim 19, -COM²- is a group of the formula

R¹¹⁶ and R¹¹⁷ are each, independently, H, C₁-C₁₈alkyl, which canoptionally be interrupted by O, or C₁-C₁₈alkoxy, which can optionally beinterrupted by O, R¹¹⁹ and R¹²⁰ are each, independently, H, C₁-C₁₈alkyl,which can optionally be interrupted by O, or R¹¹⁹ and R¹²⁰ together forma group of the formula ═CR¹⁰⁰R¹⁰¹, R¹⁰⁰ and R¹⁰¹ are each,independently, H, C₁-C₁₈alkyl, or R¹¹⁹ and R¹²⁰ together form a five orsix membered ring, which optionally can be substituted by C₁-C₁₈alkyl.14. The polymer according to claim 13, wherein the polymer is aco-polymer of the formula:*A_(o)* *COM²_(p)_(q)* *COM¹_(r)* *COM²_(s)_(t)*  (VIIc)wherein A, COM¹ and COM² are as defined in claim 13, o is 1, p is 0 or1, q is 0.005 to 1, r is 0 or 1, s is 0 or 1, and t is 0.995 to O.
 15. Apolymer consisting of repeating units of the formula:

wherein R¹ and R² are each, independently, C₁-C₂₅alkyl, R³ and R^(3′)are each, independently, C₆-C₂₅alkyl, which may optionally beinterrupted by one or more oxygen atoms, R⁴ and R^(4′) are each,independently, C₆-C₂₅alkyl, which may optionally be interrupted by oneor more oxygen atoms, and R⁷ and R^(7′) are each, independently,C₆-C₂₅alkyl, which may optionally be interrupted by one or more oxygenatoms.
 16. The polymer according to claim 15, comprising repeating unitsof the formula:

wherein R¹ and R² are each, independently, C₁-C₂₅alkyl, R³ and R^(3′)are each, independently, C₆-C₂₅alkyl, which may optionally beinterrupted by one or more oxygen atoms, R⁴ and R^(4′) are each,independently, C₆-C₂₅alkyl, which may optionally be interrupted by oneor more oxygen atoms, and R⁷ and R^(7′) are each, independently,C₆-C₂₅alkyl, which may optionally be interrupted by one or more oxygenatoms.
 17. A semiconductor device, comprising a polymer according toclaim
 11. 18. The semiconductor device according to claim 17, which is adiode, a photodiode, an organic field effect transistor and/or a solarcell, or a device containing a diode and/or a photodiode and/or anorganic field effect transistor, and/or a solar cell.
 19. Thesemiconductor device according to claim 17, which is a solar cell,comprising in this order: (a) a cathode, (b) optionally, a transitionlayer, (c) a photoactive layer, (d) optionally a smoothing layer, (e) ananode, and (f) a substrate, wherein the photoactive layer comprises saidpolymer.
 20. The semiconductor device according to claim 19, whichcomprises the transition layer and the transition layer comprises analkali halogenide.
 21. The semiconductor device according to claim 20,wherein the alkali halogenide is lithium fluoride.
 22. The semiconductordevice according to claim 17, which is a thin film transistor device,comprising: a plurality of electrically conducting gate electrodesdisposed on a substrate; a gate insulator layer disposed on saidelectrically conducting gate electrodes; a plurality of sets ofelectrically conductive source and drain electrodes disposed on saidinsulator layer such that each of said sets is in alignment with each ofsaid gate electrodes; an organic semiconductor layer disposed in thechannel between source and drain electrodes on said insulator layersubstantially overlapping said gate electrodes, wherein said organicsemiconductor layer comprises said polymer.
 23. A process for thepreparation of the organic semiconductor device according to claim 17,comprising applying a solution and/or dispersion of the polymer in anorganic solvent to a suitable substrate and removing the solvent.
 24. Amonomer of the formula:

wherein B and C are each, independently, an optionally condensedaromatic, or heteroaromatic ring, a, b, c, d, e and f are each,independently, 0, 1, 2, or 3; Ar¹ and Ar^(1′) are each, independently, agroup of formula:

Ar², Ar^(2′), Ar³, Ar^(3′), Ar⁴ and Ar^(4′) are each, independently, agroup of formula:

p is 0, 1, 2, 3 or 4, if possible, R¹ and R², which may be the same ordifferent, are hydrogen, a C₁-C₂₅alkyl group, an alkenyl group, analkynyl group, which may optionally be substituted by E and/orinterrupted by D, an allyl group, which can be substituted one to threetimes with C₁-C₄alkyl, a cycloalkyl group, which can be substituted oneto three times with C₁-C₈alkyl, C₁-C₈thioalkoxy, or C₁-C₈alkoxy, or acycloalkyl group, which can be condensed one or two times by phenyl,which can be substituted one to three times with C₁-C₄-alkyl, halogen,nitro or cyano, a cycloalkenyl group, a ketone or aldehyde group, anester group, a carbamoyl group, a silyl group, a siloxanyl group, Ar¹⁰or —CR⁵R⁶—(CH₂)_(g)—Ar¹⁰, R⁵ and R⁶ are each, independently, hydrogen,fluorine, cyano or C₁-C₄alkyl, which can be substituted by fluorine,chlorine or bromine, or phenyl, which can be substituted one to threetimes with C₁-C₄alkyl, Ar¹⁰ is aryl or heteroaryl, which may optionallybe substituted by G, which can be substituted one to three times withC₁-C₈alkyl, C₁-C₈thioalkoxy, and/or C₁-C₈alkoxy, g is 0, 1, 2, 3 or 4,R³, which may be the same or different within one group, is selectedfrom C₁-C₂₅alkyl, which may optionally be substituted by E and/orinterrupted by D, C₆-C₂₄aryl, which may optionally be substituted by G,C₂-C₂₀heteroaryl, which may optionally be substituted by G,C₁-C₁₈alkoxy, which may optionally be substituted by E and/orinterrupted by D, C₇-C₂₅aralkyl, wherein ar (=aryl) of aralkyl mayoptionally be substituted by G, or —CO—R²⁸, or two or more groups R³which are adjacent to each other, form a ring; R⁴, R^(4′), R⁷ and R^(7′)are each, independently, hydrogen, C₁-C₂₅alkyl, which may optionally besubstituted by E and/or interrupted by D, C₆-C₂₄aryl, which mayoptionally be substituted by G, C₂-C₂₀heteroaryl, which may optionallybe substituted by G, C₁-C₁₈alkoxy, which may optionally be substitutedby E and/or interrupted by D, C₇-C₂₅aralkyl, wherein ar (=aryl) ofaralkyl may optionally be substituted by G, or —CO—R²⁸; or R⁴ and R^(4′)form a ring, D is —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —CR²³=CR²⁴—, or—C≡C—, E is —OR²⁹, —SR²⁹, —NR²⁵R²⁶, —COR²⁸, —COOR²⁷, —CONR²⁵R²⁶, —CN, orhalogen, G is E, C₁-C₁₈alkyl, which may be interrupted by D, orC₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, R²³,R²⁴, R²⁵ and R²⁶ are each, independently, H, C₆-C₁₈aryl, C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, C₁-C₁₈alkyl, orC₁-C₁₈alkyl which is interrupted by —O—, R²⁷ and R²⁸ are each,independently, H, C₆-C₁₈aryl, C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₈alkoxy, C₁-C₁₈alkyl or C₁-C₁₈alkyl which isinterrupted by —O—, R²⁹ is H, C₆-C₁₈aryl, C₆-C₁₈aryl, which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, C₁-C₁₈alkyl or C₁-C₁₈alkylwhich is interrupted by —O—, R¹⁰⁹ and R¹¹⁰ are each, independently, H,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, or C₇-C₂₅aralkyl, or R¹⁰⁹ and R¹¹⁰ togetherform a group of formula ═CR¹⁰⁰R¹⁰¹, R¹⁰⁰ and R¹⁰¹ are each,independently, H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by Eand/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted byG, or C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G,or R¹⁰⁹ and R¹¹⁰ together form a five or six membered ring, whichoptionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl whichis substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D,C₇-C₂₅aralkyl, or —C(═O)—R²⁸, R¹¹¹ is H, a C₁-C₂₅alkyl group, aC₄-C₁₈cycloalkyl group, a C₁-C₂₅alkoxy group, in which one or morecarbon atoms which are not adjacent to each other could be replaced by—O—, —S—, or —C(═O)—O—, and/or wherein one or more hydrogen atoms can bereplaced by F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein oneor more carbon atoms can be replaced by O, S, or N, and/or which can besubstituted by one or more non-aromatic groups m can be the same ordifferent at each occurrence and is 0, 1, 2, or 3, X¹ is a hydrogenatom, or a cyano group, X is ZnX¹² or —SnR²⁰⁷R²⁰⁸R²⁰⁹, R²⁰⁷, R²⁰⁸ andR²⁰⁹ are identical or different and are H or C₁-C₆alkyl, wherein tworadicals optionally form a common ring and these radicals are optionallybranched or unbranched and X¹² is a halogen atom; or —OS(O)₂CF₃,—OS(O)₂-aryl, —OS(O)₂CH₃, —B(OH)₂, —B(OY¹)₂,

 —BF₄Na, or —BF₄K, Y¹ is independently in each occurrence a C₁-C₁₀alkylgroup, Y² is independently in each occurrence a C₂-C₁₀alkylene group,with the proviso that, if Ar¹ and Ar^(1′) are a group of formula

 a and d are not
 0. 25. The monomer of claim 24, wherein Y² isindependently in each occurrence —CY³Y⁴—CY⁵Y⁶— or—CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ andY¹² are each, independently, hydrogen or a C₁-C₁₀alkyl group.
 26. Themonomer of claim 25, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ andY¹² are independently of each other hydrogen, —C(CH₃)₂C(CH₃)₂—, or—C(CH₃)₂CH₂C(CH₃)₂—.
 27. A process for preparing polymers of theformula:A-COM¹  (VIId),orA-COM²  (VIIe), comprising reacting a dihalogenide, with an equimolaramount of a diboronic acid or diboronate corresponding to formulaX¹¹COM¹X¹¹,orX¹¹COM²X¹¹ under the catalytic action of Pd and triphenylphosphine,wherein A is a repeating unit of formula I:

wherein a, b, c, d, e and f are each, independently, 0, 1, 2, or 3, Ar¹and A^(1′) are each, independently, a group of formula:

Ar², Ar^(2′), Ar³, Ar^(3′), Ar⁴ and Ar^(4′) are each, independently, agroup of the formula:

p is 0, 1, 2, 3 or 4, if possible, R¹ and R², which may be the same ordifferent, are hydrogen, a C₁-C₂₅alkyl group, an alkenyl group, analkynyl group, which may optionally be substituted by E and/orinterrupted by D, an allyl group, which can be substituted one to threetimes with C₁-C₄alkyl, a cycloalkyl group, which can be substituted oneto three times with C₁-C₈alkyl, C_(r) C₈thioalkoxy, or C₁-C₈alkoxy, or acycloalkyl group, which can be condensed one or two times by phenyl,which can be substituted one to three times with C₁-C₄-alkyl, halogen,nitro or cyano, a cycloalkenyl group, a ketone or aldehyde group, anester group, a carbamoyl group, a silyl group, a siloxanyl group, Ar¹⁰or —CR⁵R⁶—(CH₂)_(g)—Ar¹⁰, R⁵ and R⁶ are each, independently, hydrogen,fluorine, cyano or C₁-C₄alkyl, which can be substituted by fluorine,chlorine or bromine, or phenyl, which can be substituted one to threetimes with C₁-C₄alkyl, Ar¹⁰ is aryl or heteroaryl, which may optionallybe substituted by G, which can be substituted one to three times withC₁-C₅alkyl, C₁-C₈thioalkoxy, and/or C₁-C₈alkoxy, g is 0, 1, 2, 3 or 4,R³, which may be the same or different within one group, is selectedfrom C₁-C₂₅alkyl, which may optionally be substituted by E and/orinterrupted by D, C₆-C₂₄aryl, which may optionally be substituted by G,C₂-C₂₀heteroaryl, which may optionally be substituted by G,C₁-C₁₈alkoxy, which may optionally be substituted by E and/orinterrupted by D, C₇-C₂₅aralkyl, wherein ar (=aryl) of aralkyl mayoptionally be substituted by G, or —CO—R²⁸, or two or more groups R³which are adjacent to each other, form a ring; R⁴, R^(4′), R⁷ and R^(7′)are each, independently, hydrogen, C₁-C₂₅alkyl, which may optionally besubstituted by E and/or interrupted by D, C₆-C₂₄aryl, which mayoptionally be substituted by G, C₂-C₂₀heteroaryl, which may optionallybe substituted by G, C₁-C₁₈alkoxy, which may optionally be substitutedby E and/or interrupted by D, C₇-C₂₅aralkyl, wherein ar (=aryl) ofaralkyl may optionally be substituted by G, or —CO—R²⁸; or R⁴ and R^(4′)form a ring, D is —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —NR²⁵—,—CR²³═CR²⁴—, or —C≡C—, E is —OR²⁹, —SR²⁹, —NR²⁵R²⁶, —COR²⁸, —COOR²⁷,—CONR²⁵R²⁶, —CN, or halogen, G is E, C₁-C₁₈alkyl, which may beinterrupted by D, or C₁-C₁₈alkoxy which is substituted by E and/orinterrupted by D, R²³, R²⁴, R²⁵ and R²⁶ are each, independently, H,C₆-C₁₈aryl, C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy, C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by —O—,R²⁷ and R²⁸ are each, independently, H, C₆-C₁aryl, C₆-C₁₈aryl which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, C₁-C₁₈alkyl or C₁-C₁₈alkylwhich is interrupted by —O—, R²⁹ is H, C₆-C₁₈aryl, C₆-C₁₈aryl, which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, C₁-C₁₈alkyl or C₁-C₁₈alkylwhich is interrupted by —O—, R¹⁰⁹ and R¹¹⁰ are each, independently, H,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, or C₇-C₂₅aralkyl, or R¹⁰⁹ and R¹¹⁰ togetherform a group of formula ═CR¹⁰⁰R¹⁰¹, R¹⁰⁰ and R¹⁰¹ are each,independently, H, C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, orC₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G, or R¹⁰⁹and R¹¹⁰ together form a five or six membered ring, which optionally canbe substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by Eand/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted byG, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, C₇-C₂₅aralkyl, or C(═O)—R²⁸,R¹¹¹ is H, a C₁-C₂₅alkyl group, a C₄-C₁₈cycloalkyl group, a C₁-C₂₅alkoxygroup, in which one or more carbon atoms which are not adjacent to eachother could be replaced by —O—, —S—, or —C(═O)—O—, and/or wherein one ormore hydrogen atoms can be replaced by F, a C₆-C₂₄aryl group, or aC₆-C₂₄aryloxy group, wherein one or more carbon atoms can be replaced byO, S, or N, and/or which can be substituted by one or more non-aromaticgroups R¹¹¹, m can be the same or different at each occurrence and is 0,1, 2, or 3, X¹ is a hydrogen atom, or a cyano group, with the provisothat, if Ar¹ and Ar^(1′) are a group of the formula

then a and d are not 0, -COM¹- is a repeating unit of the formula:

R⁷ and R^(7′) are as defined above, R⁴⁴ and R⁴¹ are hydrogen,C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, R⁴⁵ is H, C₁-C₁₈alkyl, or C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, wherein D and E areas defined above, -COM²- is a group of the formula

R¹¹⁶ and R¹¹⁷ are each, independently, H, C₁-C₁₈alkyl, which canoptionally be interrupted by O, or C₁-C₁₈alkoxy, which can optionally beinterrupted by O, R¹¹⁹ and R¹²⁰ are each, independently, H, C₁-C₁₈alkyl,which can optionally be interrupted by O, or R¹¹⁹ and R¹²⁰ together forma group of the formula ═CR¹⁰⁰R¹⁰¹, R¹⁰⁰ and R¹⁰¹ are each,independently, H, C₁-C₁₈alkyl, or R¹¹⁹ and R¹²⁰ together form a five orsix membered ring, which optionally can be substituted by C₁-C₁₈alkyl,X¹¹ is independently in each occurrence —B(OH)₂, —B(OY¹)₂ or

wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group andY² is independently in each occurrence a C₂-C₁₀alkylene group.
 28. Amonomer of formula X-A-X, wherein A is a group of formula

X is halogen, whereinAr⁴_(c)Ar³_(b)Ar²_(a)—Ar¹—and—Ar^(1′)Ar^(2′)_(d)Ar^(3′)_(e)Ar^(4′)_(f)—  may be the same ordifferent, and are a group of formula

indicates the bond to the diketopyrrolopyrrole skeleton, and R⁴ isC₆-C₂₅alkyl, which may optionally be substituted by E and/or interruptedby D, C₆-C₁₄aryl, which may optionally be substituted by G,C₁-C₂₅alkoxy, which may optionally be substituted by E and/orinterrupted by D, or C₇-C₁₅aralkyl, wherein ar may optionally besubstituted by G, D is —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, or —NR²⁵—,R²⁵ is C₁-C₁₂alkyl, E is OR²⁹, —SR²⁹, —NR²⁵R²⁵, —COR²⁸, —COOR²⁷,—CONR²⁵R²⁵, or —CN, R²⁵, R²⁷, R²⁸ and R²⁹ are each, independently,C₁-C₁₂alkyl or C₆-C₁₄ aryl, G is E or C₁-C₁₈alkyl, and R^(4′) has themeaning of R⁴, and R¹ and R², which may be the same or different, arehydrogen, a C₁-C₂₅alkyl group, an alkenyl group, an alkynyl group, whichmay optionally be substituted by E and/or interrupted by D, an allylgroup, which can be substituted one to three times with C₁-C₄alkyl, acycloalkyl group, which can be substituted one to three times withC₁-C₈alkyl, C₁-C₈thioalkoxy, or C₁-C₈alkoxy, or a cycloalkyl group,which can be condensed one or two times by phenyl, which can besubstituted one to three times with C₁-C₄-alkyl, halogen, nitro orcyano, a cycloalkenyl group, a ketone or aldehyde group, an ester group,a carbamoyl group, a silyl group, a siloxanyl group, Ar¹⁰ or—CR⁵R⁶—(CH₂)_(g)—Ar¹⁰, R⁵ and R⁶ are each, independently, hydrogen,fluorine, cyano or C₁-C₄alkyl, which can be substituted by fluorine,chlorine or bromine, or phenyl, which can be substituted one to threetimes with C₁-C₄alkyl, Ar¹⁰ is aryl or heteroaryl, which may optionallybe substituted by G, which can be substituted one to three times withC₁-C₈alkyl, C₁-C₈thioalkoxy, and/or C₁-C₈alkoxy, g is 0, 1, 2, 3 or 4.29. The monomer according to claim 28, wherein A is a group of formula:

wherein R¹ and R² are each, independently, C₁-C₂₅alkyl, and R⁴ isC₆-C₂₅alkyl, which may optionally be interrupted by one or more oxygenatoms.
 30. A method of making a product, comprising incorporating thepolymer of claim 11 into the product.
 31. The method of claim 30,wherein the product is selected from the group consisting ofcharge-transport material, semiconducting material, electroluminescentconducting material, photoconducting material, light emitting material,surface-modifying material, electrode materials in batteries, alignmentlayers, or in OFETs, ICs, TFTs, displays, RFITD tags, electro- orphotoluminescent devices, backlights of displays, photovoltaic or sensordevices, charge injection layers, Schottky diodes, memory devices,planarising layers, antistatics, conductive substrates or patterns,photoconductors, and electrophotographic applications.
 32. A polymerconsisting of repeating unit(s) of the formula:

R¹ and R², which may be the same or different, are hydrogen, aC₁-C₂₅alkyl group, an alkenyl group, an alkynyl group, which mayoptionally be substituted by E and/or interrupted by D, an allyl group,which can be substituted one to three times with C₁-C₄alkyl, acycloalkyl group, which can be substituted one to three times withC₁-C₅alkyl, C₁-C₈thioalkoxy, or C₁-C₈alkoxy, or a cycloalkyl group,which can be condensed one or two times by phenyl, which can besubstituted one to three times with C₁-C₄-alkyl, halogen, nitro orcyano, a cycloalkenyl group, a ketone or aldehyde group, an ester group,a carbamoyl group, a silyl group, a siloxanyl group, Ar¹⁰ or—CR⁵R⁶—(CH₂)_(g)—Ar¹⁰, R⁴ are each, independently, hydrogen,C₁-C₂₅alkyl, which may optionally be substituted by E and/or interruptedby D, C₆-C₂₄aryl, which may optionally be substituted by G,C₂-C₂₀heteroaryl, which may optionally be substituted by G,C₁-C₂₅alkoxy, which may optionally be substituted by E and/orinterrupted by D, C₇-C₂₅aralkyl, wherein ar (=aryl) of aralkyl mayoptionally be substituted by G, or —CO—R²⁸; wherein D is —CO—, —COO—,—S—, —SO—, —SO₂—, —O—, or —NR²⁵—, R²⁵ is C₁-C₁₂alkyl, E is OR²⁹, —SR²⁹,—NR²⁵R²⁵, —COR²⁸, —COOR²⁷, —CONR²⁵R²⁵, or —CN, R²⁵, R²⁷, R²⁸ and R²⁹ areeach, independently, C₁-C₁₂alkyl or C₆-C₁₄ aryl, and G is E orC₁-C₁₈alkyl R⁵ and R⁶ are each, independently, hydrogen, fluorine, cyanoor C₁-C₄alkyl, which can be substituted by fluorine, chlorine orbromine, or phenyl, which can be substituted one to three times withC₁-C₄alkyl, Ar¹⁰ is aryl or heteroaryl, which may optionally besubstituted by G, and g is 0, 1, 2, 3 or
 4. 33. A polymer consisting ofrepeating units of the formula

wherein n is an integer of 2 or more.